JP5946618B2 - Binder for manufacturing inorganic fiber products, manufacturing method thereof, and manufacturing method of inorganic fiber products - Google Patents

Description

  The present invention relates to a binder used for producing an inorganic fiber product and a method for producing the inorganic fiber product.

Conventionally, inorganic fiber products formed by bonding inorganic fibers such as glass wool, rock wool, and ceramic fibers with a binder are used for heat insulating materials, sound absorbing materials, and other various molded products (automobile roofs, bonnet liners, etc.). ing.
In general, inorganic fiber products are produced by attaching a binder to inorganic fibers and accumulating them to obtain an aggregate in the shape of the desired inorganic fiber product, followed by heating and curing the binder. As a binder, a resin mainly composed of a phenol resin obtained by a reaction between phenols and aldehydes (hereinafter sometimes referred to as a phenol resin binder) is relatively inexpensive and has performance such as mechanical strength. Widely used because excellent products can be obtained.
However, when a phenol resin binder is used, there are problems that unreacted aldehydes and phenols are volatilized in the production process, deteriorating the working environment, and formaldehyde is diffused from the resulting inorganic fiber product. Aldehydes are substances that adversely affect the human body. For example, formaldehyde released from building materials is considered to be one of the causative substances of sick house syndrome. For this reason, in 2003, the revised Building Standards Law, which regulates the amount of formaldehyde emitted, was enforced. Under the revised Building Standards Law, formaldehyde emission rate of 5 μg / m ² · h or less as the formaldehyde emission rate measured according to JIS A1901 is not regulated, so formaldehyde emission rate is 5 μg even for inorganic fiber products. / M ² · h or less is desired.

As one of countermeasures for the problem that aldehydes are volatilized in the manufacturing process of inorganic fiber products (when the binder is sprayed, etc.), phenol resin is modified with urea. In this case, the aldehydes in the phenol resin are captured by urea introduced into the phenol resin, and the volatilization amount of the aldehydes in the manufacturing process is reduced, thereby improving the working environment.
As one of the countermeasures for the problem of phenol volatilization in the manufacturing process of inorganic fiber products (when binder is sprayed, etc.), it is adjusted by the molar ratio of phenols and aldehydes at the time of phenol resin production and the progress of the reaction. There is a way.
As a countermeasure against the problem of formaldehyde being diffused from inorganic fiber products, it is now common to use formaldehyde scavengers such as ethylene urea and adipic acid dihydrazide together (for example, see Patent Document 1). The formaldehyde scavenger reacts with the generated formaldehyde and immobilizes it to reduce formaldehyde emission.

JP 2001-178805 A

However, in the conventional method, it is difficult to produce an inorganic fiber product at a low cost with less volatilization of phenols and aldehydes in the production process, a good working environment, a small amount of formaldehyde emission, and good performance. .
For example, a method of modifying a phenol resin with urea is effective in reducing the volatilization amount of aldehydes in the production process, but the formaldehyde emission amount from the obtained inorganic fiber product tends to increase. This is presumably because the formaldehyde source is fixed in the inorganic fiber product, stays as latent formaldehyde, and is re-released by hydrolysis or the like. In addition, when a phenol resin modified with urea is used as a binder, there is a problem that the performance of the obtained inorganic fiber product, such as water resistance, is lower than when a phenol resin not modified with urea is used. is there.
Although the use of formaldehyde scavengers is effective in reducing the amount of formaldehyde diffused, conventional formaldehyde scavengers are more expensive than phenolic resins, and the formaldehyde stripping rate is at a level of 5 μg / m ² · h or less. If an attempt is made to obtain an inorganic fiber product having a low formaldehyde emission amount, the amount of use increases, leading to an increase in cost, and the cost merit of the phenol resin binder is impaired. Moreover, since the formaldehyde scavenger is usually added after curing as described in Patent Document 1, it leads to complication of the process. Therefore, a phenol resin binder that can obtain an inorganic fiber product with a small amount of formaldehyde emission without using the formaldehyde scavenger is required.

  The present invention has been made in view of the above circumstances, and since there is little volatilization of phenols and aldehydes in the production process, the work environment is not deteriorated, and an inorganic fiber product with low formaldehyde emission amount and good performance is obtained. It aims at providing the manufacturing method of the binder and inorganic fiber product which can be manufactured at low cost.

As a result of intensive studies, the present inventors blended a phenol resin (which may be urea-modified) and a saccharide produced using sodium hydroxide as a catalyst at a specific ratio, and used this as a binder. It has been found that the above-mentioned problems can be solved by the use, and the present invention has been completed.
The present invention for solving the above problems has the following aspects.
[1] contains phenolic resin and carbohydrate,
The phenol resin is obtained by reacting phenols and aldehydes containing formaldehydes in the presence of sodium hydroxide,
The ratio x (mass%) of the saccharide to the total amount of the nonvolatile content of the phenol resin and the saccharide, and the molar ratio (aldehydes / phenols) y of the phenols and the aldehydes are represented by the following formula 1. A binder for producing inorganic fiber products satisfying ~ 3.
Formula 1: y ≦ −25 / (x + 10) +3.8
Formula 2: y ≧ −0.012x + 1.9
Formula 3: 30 ≦ x ≦ 90
[2] A first agent containing a phenol resin and a second agent containing a saccharide,
The phenol resin is obtained by reacting phenols and aldehydes containing formaldehydes in the presence of sodium hydroxide,
The ratio x (mass%) of the saccharide to the total amount of the nonvolatile content of the phenol resin and the saccharide, and the molar ratio (aldehydes / phenols) y of the phenols and the aldehydes are represented by the following formula 1. A binder for producing inorganic fiber products satisfying ~ 3.
Formula 1: y ≦ −25 / (x + 10) +3.8
Formula 2: y ≧ −0.012x + 1.9
Formula 3: 30 ≦ x ≦ 90
[3] A step of reacting a phenol with an aldehyde containing formaldehyde in the presence of sodium hydroxide to obtain a phenol resin;
Mixing the phenolic resin and sugar to obtain a binder for producing inorganic fiber products ,
The ratio x (mass%) of the saccharide to the total amount of the nonvolatile content of the phenol resin and the saccharide, and the molar ratio (aldehydes / phenols) y of the phenols and the aldehydes are represented by the following formula 1. The manufacturing method of the binder for inorganic fiber products manufacture which satisfy | fills ~ 3 .
Formula 1: y ≦ −25 / (x + 10) +3.8
Formula 2: y ≧ −0.012x + 1.9
Formula 3: 30 ≦ x ≦ 90
[ 4 ] A method for producing an inorganic fiber product, comprising the steps of attaching the inorganic fiber product-producing binder according to [1] to an inorganic fiber and molding the inorganic fiber product to obtain an inorganic fiber product.
[ 5 ] A step of obtaining an inorganic fiber product by mixing the inorganic agent with the first agent and the second agent of the binder for producing an inorganic fiber product according to [2] or simultaneously adhering to the inorganic fiber and molding. Manufacturing method of inorganic fiber products.

  According to the present invention, a binder and an inorganic fiber product that can produce an inorganic fiber product with a low formaldehyde emission amount and good performance at low cost without deteriorating the working environment because there is little volatilization of phenols and aldehydes in the production process. Can be provided.

y = −25 / (x + 10) +3.8, y = −0.012x + 1.9 and x = 90 lines, Reference Example 1 , Examples 2 to 4, Reference Examples 6 to 7, Examples 8 to 18, The graph which plotted the coordinate (x, y) determined by the value of x of each of Reference Examples 19-20, Examples 21-28, and Comparative Examples 1-22 (horizontal axis: x, vertical axis: y). ○ indicates the coordinates of the examples and the coordinates of the reference examples, and the numerical values attached to the circles indicate the example numbers and the reference example numbers . X shows the coordinate of a comparative example, and the numerical value attached | subjected to x shows a comparative example number.

<Binder for manufacturing inorganic fiber products>
A first embodiment of a binder for producing an inorganic fiber product of the present invention (hereinafter sometimes simply referred to as a binder) contains a phenol resin and a saccharide, and the phenol resin contains an aldehyde containing phenols and formaldehydes. In the presence of sodium hydroxide, the ratio x (mass%) of the saccharide to the total amount of the non-volatile content of the phenol resin and the saccharide, the phenols and The molar ratio (aldehydes / phenols) y of the aldehydes satisfies the following formulas 1 to 3.
Formula 1: y ≦ −25 / (x + 10) +3.8
Formula 2: y ≧ −0.012x + 1.9
Formula 3: x ≦ 90

In FIG. 1, y = −25 / (x + 10) +3.8, y = −0.012x + 1.9 and x = 90 lines, Reference Example 1 described later , Examples 2-4, Reference Examples 6-7, A graph (horizontal axis: x, vertical axis) in which coordinates (x, y) determined by the values of x and y in Examples 8 to 18, Reference Examples 19 to 20, Examples 21 to 28, and Comparative Examples 1 to 22 are plotted. : Y).
As shown in FIG. 1, the range satisfying the above equations 1 to 3 is that the coordinates (x, y) are y = −25 / (x + 10) +3.8, y = −0.012x + 1.9, and x = 90. Indicates the area enclosed by the line.
Hereinafter, the value of x at the intersection of y = −25 / (x + 10) +3.8 and y = −0.012x + 1.9 is referred to as x ₁ , and the value of y is referred to as y ₁ .
The expression y = −25 / (x + 10) +3.8 indicates an upper limit value that y can take when x is a predetermined value (where x ₁ <x ≦ 90), and y is a predetermined value (where y The lower limit value that x can take when ≧ y ₁ ) is shown.
Expression −0.012x + 1.9 indicates the lower limit of the range that y can take when x is a predetermined value (where x ₁ <x ≦ 90), and y is a predetermined value (where y ≦ y ₁ ). The lower limit of the range that x can take is shown.
possible range of x is wider y is close to _{y 1,} most particularly widened when _{y = y 1 (x 1 ≦} x ≦ 90). That is, the molar ratio of aldehyde / phenol of a phenolic resin which may be used is closer to y _1, a range of sugar mass which may be blended to the phenolic resin is widened.
On the other hand, the possible range of y is wider as x is closer to 90, and is the widest when x = 90 (0.82 ≦ y ≦ 3.55). In other words, the higher the ratio of carbohydrate to phenolic resin, the wider the range of aldehydes / phenols molar ratios that can be used.

Since x and y satisfy | fill said Formulas 1-3, since the volatilization amount of phenols and aldehydes in a manufacturing process can be reduced, a working environment becomes favorable. In addition, an inorganic fiber product having a small formaldehyde emission rate of, for example, 5 μg / m ² · h or less as a formaldehyde emission rate and good performance can be produced at low cost.
In the present specification, the formaldehyde emission rate is a value measured according to JIS A1901.
On the other hand, if the value of y is too large (does not satisfy Formula 1), a large amount of unreacted aldehydes (free aldehydes) remain, so during the process of manufacturing inorganic fiber products (at the time of adhesion, at the time of curing, etc.) In addition, the free aldehydes and aldehydes generated by the condensation reaction may be volatilized. Moreover, in the obtained inorganic fiber product, a formaldehyde source is latent, and there is a risk of increasing the amount of formaldehyde emitted from the inorganic fiber product.
If the value of y is too small (does not satisfy Formula 2), problems such as odor generation and yield reduction due to volatilization of unreacted phenols (free phenols) may occur.
Moreover, when the value of x exceeds 90 (it does not satisfy | fill Formula 3), there exists a possibility that performances, such as water resistance strength of the inorganic fiber product obtained, may deteriorate.
If the value of x is too small (one or both of formulas 1 and 2 are not satisfied), the amount of formaldehyde emitted from the inorganic fiber product may not be sufficiently reduced.

The second aspect of the binder of the present invention comprises a first agent containing a phenol resin and a second agent containing a saccharide, and the phenol resin hydroxylates phenols and aldehydes containing formaldehydes. It is obtained by reacting in the presence of sodium, and the ratio x (mass%) of the saccharide to the total amount of the non-volatile content of the phenol resin and the saccharide, and the moles of the phenol and the aldehyde The ratio (aldehydes / phenols) y satisfies the above formulas 1 to 3.
The binder of the second aspect is the same as the binder of the first aspect, except that a phenol resin and a saccharide are included as separate agents.

[Phenolic resin]
The phenol resin used in the present invention is a so-called resol type phenol resin obtained by reacting phenols and aldehydes in the presence of an alkali catalyst, and using sodium hydroxide as the alkali catalyst. It is.
Examples of phenols include phenol, cresol, resorcinol, catechol, bisphenol A, xylenol, butylphenol, octylphenol, etc. Any one of them may be used alone or two or more of them may be used in combination.
At least formaldehyde is used as the aldehyde. Examples of formaldehydes include formaldehyde, paraformaldehyde, trioxane, dimethyl formal, and the like, and any one of them may be used alone or two or more of them may be used in combination.
As aldehydes, aldehydes other than formaldehyde may be used in combination. Examples of aldehydes other than formaldehydes include acetaldehyde and benzaldehyde, and any one of them may be used alone or two or more of them may be used in combination.
In the total of aldehydes, the ratio of formaldehyde is preferably 10 mol% or more, and more preferably 50 mol% or more. The upper limit of this ratio is not specifically limited, 100 mol% may be sufficient.

As for the usage-amount of sodium hydroxide at the time of making phenols and aldehydes react, 1-10 mass parts is preferable with respect to 100 mass parts of phenols. If it is 1 mass part or more, reaction will fully advance. If it is 10 mass parts or less, control of reaction is easy.
The amount of phenols and aldehydes used is set so that the molar ratio of phenols and aldehydes (aldehydes / phenols) y satisfies the above formulas 1 to 3. As described above, the upper and lower limits of the range that y can take are determined by Equations 1 and 2, respectively. For example, when x is 90 (mass%), the upper limit of the range that y can take is the value when x is 90 in Equation 1, that is, 3.55, and the lower limit is when x is 90 in Equation 2. The value is 0.82. When x is 10, the upper limit of the range that y can take is the value when x is 10 in Equation 1, that is, 2.55, and the lower limit is the value when x is 10 in Equation 2, that is, 1.78.

The reaction between phenols and aldehydes is usually performed for about 3 to 8 hours under a temperature condition of about 50 to 80 ° C.
After completion of the reaction, it is preferable to add an acid for neutralization. Examples of the acid used for neutralization include boric acid, sulfuric acid, hydrochloric acid, formic acid and the like, and any one of them may be used alone or two or more may be used in combination. The pH (23 ° C.) of the phenol resin after neutralization is preferably about 6 to 8 from the viewpoint of suppressing the change with time of the resin (stability over time).

The number average molecular weight of the phenol resin is preferably 150 to 400. When the number average molecular weight is less than 150, the content of unreacted phenols (free phenols) is large, the odor increases in the production process of inorganic fiber products, and the mechanical strength of the resulting inorganic fiber products decreases. There is a fear that it is not preferable. Moreover, when a number average molecular weight exceeds 400, the water dilutability of a phenol resin falls and it is unpreferable.
The number average molecular weight of the phenol resin can be measured by gel permeation chromatography (GPC) using polystyrene as a standard substance.

The amount of free phenols in the phenol resin is preferably 5% by mass or less. If it exceeds 5% by mass, the odor in the production process of the inorganic fiber product increases, which may increase the load on the exhaust gas treatment facility.
The amount of free aldehydes in the phenol resin is preferably 10% by mass or less. If it exceeds 10% by mass, the volatilization amount of aldehydes and the emission amount of formaldehyde from the inorganic fiber product in the inorganic fiber product production process may increase, which is not preferable.
The nonvolatile content of the phenol resin is preferably 30% by mass or more, and more preferably 40% by mass or more from the viewpoint of transportation cost.

[Sugar]
Examples of the saccharide include monosaccharides, disaccharides, oligosaccharides of three or more sugars, polysaccharides and derivatives thereof, and any of them may be used.
Examples of monosaccharides include glucose, fructose, mannose, galactose, ribose and xylose.
Examples of the disaccharide include sucrose (sucrose), maltose, lactose, trehalose, isomaltose and the like.
In the present specification, “oligosaccharides of 3 or more sugars” are those in which 3 to 10 monosaccharides are bound, and “polysaccharides” are those in which 11 or more monosaccharides are bound.
Examples of oligosaccharides having three or more sugars include trisaccharides such as maltotriose and raffinose; fructooligosaccharides, galactooligosaccharides, isomaltoligosaccharides, and the like.
Examples of the polysaccharide include starch, pullulan, dextrin, polydextrose and the like.
Examples of these derivatives include modified starches such as glycosides, esterified starches, and etherified starches.

As the saccharide, it is preferable to contain at least one selected from the group consisting of monosaccharides and disaccharides (hereinafter sometimes referred to as specific carbohydrates) from the viewpoint of excellent effects of the present invention.
Among these, as the specific carbohydrate, a monosaccharide is preferable, and at least one selected from glucose and fructose is particularly preferable.
The ratio of the specific carbohydrate in the carbohydrate is preferably 10% by mass or more, and more preferably 50% by mass or more. An upper limit is not specifically limited, 100 mass% may be sufficient. That is, the saccharide may be composed only of the specific saccharide.

The sugar used for the binder may be one type or two or more types.
The amount of the saccharide is set such that the ratio x (mass%) of the saccharide to the total amount of the non-volatile content and the saccharide of the phenol resin satisfies the above formulas 1 to 3. As described above, the upper limit of the range that x can take is determined by Equation 3. The lower limit of the range is determined by Equation 1 when y is y ₁ or more, and is determined by Equation 2 when y is y ₁ or less. For example, when y is 3, the minimum value x can take is the value when y is 3 in Equation 1, that is, 21.25. When y is 1, the lower limit of the range that x can take is the value when x is 1 in Equation 2, that is, 75.

When the binder of the present invention is a composition containing a phenol resin and a saccharide, the method for blending the phenol resin and the saccharide is not particularly limited. For example, it can be prepared by mixing the phenol resin and a saccharide.
When the binder of the present invention is a kit comprising a first agent containing a phenol resin and a second agent containing a saccharide, the first agent and the second agent are usually used because of easy adhesion to inorganic fibers. Both agents are preferably aqueous solutions. The phenol resin obtained by reacting phenols and aldehydes in the presence of sodium hydroxide is usually in the form of an aqueous solution, which may be used as the first agent as it is, and the resin concentration (non-volatile content) is appropriately selected. ) For adjusting water (adjusted water) may be added. As the aqueous solution of the saccharide as the second agent, a commercially available solution may be used, or a commercially available solid saccharide or an aqueous solution of saccharide may be added to obtain an aqueous solution having a predetermined saccharide concentration. Good.

[Other optional ingredients]
In the binder of the present invention, if necessary, other components other than the phenol resin and the saccharide may be blended within a range not impairing the effects of the present invention.
When the binder of the present invention is a kit comprising a first agent and a second agent, the other components may be blended in either the first agent or the second agent. Moreover, you may combine with a 1st agent and a 2nd agent as another agent.
The other components can be appropriately selected from those known as components that can be blended in the binder of inorganic fiber products. For example, urea, melamine, dicyandiamide, ammonia, curing accelerator, silane coupling agent, known Formaldehyde scavenger, water repellent, dust-preventing oil, water and the like. These may be used alone or in combination of two or more.

Among the above optional components, when blending at least one selected from urea, melamine, and dicyandiamide (hereinafter referred to as DCDA), the volatilization amount of aldehydes during the production process of the inorganic fiber product is reduced as compared with the case of not blending. Can be reduced.
Conventionally, a phenol resin modified with urea (a mixture of phenol resin mixed with urea or a reaction product obtained by reacting them) has been used as a binder for inorganic fiber products, but it has not been modified. Compared to the case of using a phenol resin, the amount of formaldehyde emitted from the resulting inorganic fiber product tends to increase in contrast to the amount of volatilization of aldehydes in the production process. However, an inorganic fiber product with a small amount of formaldehyde emission can be obtained.
5-100 mass% is preferable with respect to the non volatile matter (100 mass%) of a phenol resin, and, as for the compounding quantity of at least 1 sort (s) chosen from urea, a melamine, and DCDA, 10-70 mass% is more preferable. If it is 5% by mass or more, the effect of reducing the volatilization amount of aldehydes can be sufficiently obtained. If it exceeds 100% by mass, the resulting inorganic fiber product may have insufficient performance such as water resistance, and may lead to an increase in the amount of formaldehyde emitted from the obtained inorganic fiber product.
At least one compounding method selected from urea, melamine, and DCDA to phenol resin is a method of adding to phenol resin in advance, a method of adding in advance as a binder to inorganic fibers, and a method of attaching to inorganic fibers Examples include a method of pipe mixing (mixing using a line mixer or the like in the pipe) immediately before, a method of spraying inorganic fibers using a nozzle different from a nozzle for spraying a phenol resin, and the like.
When at least one selected from urea, melamine, and DCDA is added, a carbohydrate may be added to the phenol resin.
When the phenol resin is reacted with at least one selected from urea, melamine, and DCDA, the reaction condition is preferably about 30 to 300 minutes under a temperature condition of about 20 to 100 ° C. At this time, a part of at least one selected from urea, melamine, and DCDA to be blended may be reacted, and the remainder may be added by the above method.

Among the above optional components, ammonia improves the working environment by reacting with free formaldehyde in the binder and converting it to hexamine. Moreover, by mix | blending ammonia, pH of a binder increases and water dilutability improves. The improvement of water dilutability is preferable from the viewpoint of preventing adhesion of the binder to the pipe and clogging of the spray nozzle.
As for the compounding quantity of ammonia, 0-20 mass% is preferable with respect to the non volatile matter of a phenol resin.
As a method of blending ammonia, a method of adding to a phenol resin, a method of adding to a saccharide, a method of adding to a blend of a phenol resin and a saccharide, a method of adding to diluting water, other agents (phenol resin, saccharide In addition to the method of adding to the inorganic fiber as a binder, the method of adding in advance to the inorganic fiber as a binder, the method of adding to the phenolic resin by pipe mixing just before attaching to the inorganic fiber, and a nozzle that sprays the phenolic resin Examples include a method of spraying on inorganic fibers. However, when ammonia is added to a phenolic resin or when it is added to a blend of a phenolic resin and a sugar, the time-dependent change of the phenolic resin is accelerated due to the increase in pH. The shorter the time until it is made, the better. Therefore, as a blending method, mixing immediately before use, pipe mixing, and spraying with another nozzle are particularly preferable.
At the time of mixing ammonia, the phenol resin may be modified with at least one selected from urea, melamine, and DCDA.

The curing accelerator is used for accelerating the curing of the binder, and particularly preferably used when urea is blended.
Examples of the curing accelerator include ammonium salts such as ammonium sulfate, ammonium chloride, and ammonium phosphate.
As for the compounding quantity of a hardening accelerator, 0-3 mass% is preferable with respect to the non volatile matter of a phenol resin.
As a method of blending the curing accelerator, a method of adding to a phenol resin, a method of adding to a saccharide, a method of adding to a blend of a phenol resin and a saccharide, a method of adding to dilution water, other agents (phenol resin, Aside from the method of adding to carbohydrates and dilution water, the method of adding in advance to the inorganic fiber as a binder, the method of adding to the phenolic resin by pipe mixing just before attaching to the inorganic fiber, and the nozzle spraying the phenolic resin The method of spraying on an inorganic fiber with a nozzle, etc. are mentioned. However, when adding a curing accelerator to a phenol resin, or when adding it to a blend of a phenol resin and a carbohydrate, the time-dependent change of the phenol resin becomes faster. The shorter the time until it is made, the better. Therefore, as a blending method, mixing immediately before use, pipe mixing, and spraying with another nozzle are particularly preferable.
When blending the curing accelerator, the phenol resin may be modified with at least one selected from urea, melamine, and DCDA.

Silane coupling agents are used to improve water resistance and mechanical strength.
The silane coupling agent is not particularly limited, and examples thereof include aminosilane compounds such as N-2- (aminoethyl) -3-aminopropylmethyldimethoxysilane and 3-aminopropyltriethoxysilane.
The compounding amount of the silane coupling agent is preferably 0 to 1.0% by mass with respect to the nonvolatile content of the binder (excluding the silane coupling agent).
As a method of blending the silane coupling agent, a method of adding to a phenol resin, a method of adding to a saccharide, a method of adding to a blend of a phenol resin and a saccharide, a method of adding to diluting water, another agent (phenol resin To add to the inorganic fiber as a binder, to add to the inorganic fiber as a binder, to add to the phenolic resin by pipe mixing just before attaching to the inorganic fiber, and a nozzle to spray the phenolic resin The method of spraying on an inorganic fiber with another nozzle, etc. are mentioned. However, when adding a silane coupling agent to a phenol resin, or when adding it to a blend of a phenol resin and a carbohydrate, the aging of the phenol resin becomes faster. It is preferable that the time until adhesion is shorter. Therefore, as a blending method, mixing immediately before use, pipe mixing, and spraying with another nozzle are particularly preferable.
At the time of blending the silane coupling agent, the phenol resin may be modified with at least one selected from urea, melamine, and DCDA.

The formaldehyde scavenger is not particularly limited, and for example, a known formaldehyde scavenger as described in JP 2001-178805 A can be used.
As a blending method of the formaldehyde scavenger, a method of adding to a phenol resin, a method of adding to a saccharide, a method of adding to a blend of a phenol resin and a saccharide, a method of adding to dilution water, other agents (phenol resin, Aside from the method of adding to carbohydrates and dilution water, the method of adding in advance to the inorganic fiber as a binder, the method of adding to the phenolic resin by pipe mixing just before attaching to the inorganic fiber, and the nozzle spraying the phenolic resin The method of spraying on an inorganic fiber with a nozzle, the method of spraying on the inorganic fiber product after hardening, etc. are mentioned. Among these, the method of spraying on the cured inorganic fiber product is preferable.
At the time of formulating the formaldehyde scavenger, the phenol resin may be modified with at least one selected from urea, melamine, and DCDA.

Examples of the water repellent include a silicone water repellent and a fluorine water repellent.
Examples of the dust-preventing oil include mineral oil-based oil emulsions.
As a blending method of water repellent and dust-preventing oil, a method of adding to a phenol resin, a method of adding to a saccharide, a method of adding to a blend of a phenol resin and a saccharide, and a method of adding to dilution water, respectively. , Method to add to other agents (other than phenolic resin, saccharide, dilution water), Method to add to inorganic fiber as a binder in advance, Method to add to phenolic resin by pipe mixing just before attaching to inorganic fiber, Phenol A method of spraying inorganic fibers with a nozzle different from the nozzle for spraying resin, and the like can be mentioned. From the viewpoint of compatibility with other agents, mixing immediately before use, pipe mixing, and spraying with another nozzle are preferred.
The phenol resin may be modified with at least one selected from urea, melamine, and DCDA when the water repellent or dust-preventing oil is blended.

  As a method of blending water, a method of adding to a phenolic resin, a method of adding to a saccharide, a method of adding to a blend of a phenolic resin and a saccharide, and adding to other agents (other than phenolic resin, saccharides and diluted water) A method of adding to the inorganic fiber as a binder in advance, a method of adding to the phenolic resin by pipe mixing just before attaching to the inorganic fiber, a method of spraying the inorganic fiber with a nozzle different from the nozzle that sprays the phenolic resin, curing Examples include a method of spraying on a later inorganic fiber product, and any method may be used.

Below, the preferable mixing | blending pattern of each component which comprises the binder (1st aspect and 2nd aspect) of this invention in the case of mix | blending arbitrary components is shown. However, the present invention is not limited to these combination patterns.
Formulation pattern 1: (phenolic resin / carbohydrate) + optional component.
Formulation pattern 2: (phenolic resin / arbitrary component) + carbohydrate.
Formulation pattern 3: (carbohydrate / optional component) + phenolic resin.
Formulation pattern 4: (phenol resin / first optional component) + (sugar / second optional component).
Formulation pattern 5: (carbohydrate / first optional component) + phenol resin + second optional component.
Formulation pattern 6: (phenol resin / first optional component) + carbohydrate + second optional component.
Formulation pattern 7: (phenol resin / first optional component) + (sugar / second optional component) + third optional component.
Formulation pattern 8: phenol resin + sugar + optional component.

In each of the above patterns, the sign “+” indicates that the components before and after the sign may be attached to the inorganic fiber as a mixture or may be attached by separate spraying (simultaneous spraying, time spraying) (but before heating). .
The symbol “·” indicates that the component after the symbol is blended by the following blending method i, ii, iii or iv with respect to the component described before the symbol.
Blending method i: a method of reacting for about 30 to 300 minutes under a temperature condition of about 20 to 100 ° C.
Blending method ii: simply mixing.
Blending method iii: A method of mixing in a pipe using a line mixer or the like.
Blending method iv: A method of spraying an optional component on an inorganic fiber as a separate agent.
Arbitrary components may be used individually by 1 type, or may use 2 or more types together. When using 2 or more types together, you may mix | blend them simultaneously or with a time difference.
The first optional component, the second optional component, and the third optional component indicate optional components that are added at different timings. The first optional component, the second optional component, and the third optional component may be the same or different. Moreover, when using 2 or more types together as a 1st arbitrary component, a 2nd arbitrary component, or a 3rd arbitrary component, they may mix | blend simultaneously or with a time difference.

In the blending pattern 1, a carbohydrate is preferably blended in the phenol resin, and then optional components are blended by the following blending method i, ii, iii or iv.
In the blending pattern 2, preferably, an optional component is blended with the phenol resin by the following blending method i, ii or iii, and then a carbohydrate is blended.
In the blending pattern 3, preferably, an arbitrary component is blended with the saccharide by the blending method ii or iii below, and then a phenol resin is blended.
In the blending pattern 4, preferably, the first optional component is blended with the phenol resin by the following blending method i, ii or iii to obtain the first blend, and the second optional component is separately added to the carbohydrate. The following blending method ii or iii is blended to obtain a second blend, and then the first blend and the second blend are blended.
In the blending pattern 5, preferably, the first optional component is blended with the saccharide by the following blending method ii or iii, then the phenol resin is blended, and then the second optional component is blended.
In the blending pattern 6, preferably, the first optional component is blended with the phenol resin, then the carbohydrate is blended, and then the second optional component is blended by the following blending method i, ii, iii or iv.
In the blending pattern 7, preferably, the first optional component is blended with the phenol resin by the following blending method i, ii or iii to obtain the first blend, and the second optional component is separately added to the saccharide. The following blending method ii or iii is blended to obtain a second blend, then the first blend and the second blend are blended, and then the third optional component is blended into the following blending methods i, ii, iii Or blended by iv.
In the blending pattern 8, the phenol resin, the saccharide, and the optional component are preferably blended together by the following blending methods i, ii, iii, or iv, or sprayed separately.

According to the binder of the present invention, the volatilization of phenols and aldehydes during the production of inorganic fiber products can be reduced, and the formaldehyde emission rate is small, for example, 5 μg / m ² · h or less as the formaldehyde emission rate, and the performance is also good An inorganic fiber product is obtained.
The production of inorganic fiber products will be described in detail in the method for producing inorganic fiber products, which will be described later, but the inorganic fibers to be produced are accumulated by attaching the inorganic fibers to the inorganic fibers by spraying the binder, etc. After forming an aggregate having a shape corresponding to a textile product, the aggregate is heated (about 200 to 270 ° C.) to cure the binder.
The phenol resin used as a binder generally has a polymer skeleton formed by the reaction of phenols and formaldehyde, and usually an excess of formaldehyde is used during synthesis. Therefore, unreacted formaldehyde (free formaldehyde) remains in the obtained phenol resin. Therefore, when manufacturing an inorganic fiber product using the binder containing a phenol resin, this free formaldehyde and the formaldehyde produced by the condensation reaction volatilize during the manufacturing process (at the time of adhesion, at the time of hardening, etc.). In addition, formaldehyde sources are latent in the obtained inorganic fiber products, and formaldehyde may be diffused by hydrolysis or the like.
In the present invention, the amount of volatilization of aldehydes and phenols during the production process can be reduced by blending a saccharide with a phenol resin and setting the values of x and y so as to satisfy the above formulas 1 to 3. Moreover, emission of formaldehyde from the inorganic fiber product which is the final product can be suppressed. The reason why such an effect is obtained is not clear, but it is considered that the structure of the phenol resin, the residual amount of aldehydes and phenols, the nature of the carbohydrates, and the like act synergistically.
For example, the alkali catalyst affects the structure of the resulting phenolic resin. When sodium hydroxide is used, the addition reaction of aldehydes has a strong para (p-) orientation. On the other hand, even with the same alkali catalyst, in the case of barium hydroxide, the addition reaction of aldehydes is ortho (o-). It is said that the orientation is strong. As shown in Reference Examples a to d described later, when barium hydroxide is used as the alkali catalyst, good results may be obtained even when x and y do not satisfy the above formula. This is considered to be due to the difference in structure of the obtained phenol resin.
Moreover, although it is estimated that the saccharide | sugar mentioned above and its decomposition product are exhibiting the same function as the conventional formaldehyde scavenger, the reaction mechanism is complicated and the detail is not clear.

As mentioned above, by limiting the ratio of phenols and aldehydes used in the production of phenolic resin and the amount of saccharides added, it is possible to improve the working environment during production and reduce the amount of formaldehyde emitted from the product. By using the binder of the present invention in the production of inorganic fiber products, the amount of conventional formaldehyde scavenger used can be reduced. Moreover, carbohydrates are cheaper than conventional formaldehyde scavengers. Therefore, the manufacturing cost of inorganic fiber products can be reduced.
Furthermore, in order to reduce the amount of formaldehyde volatilization during the manufacturing process, it has been conventionally practiced to add urea to a phenolic resin as a modifying agent. There was a problem that the performance of the obtained inorganic fiber product, in particular, the water resistance strength was lowered. In the present invention, by replacing part or all of the urea compounded to the phenol resin with sugar, the amount of formaldehyde emitted from the inorganic fiber product is greatly reduced compared to the case where urea is compounded alone. Not only can it be possible to suppress deterioration in performance such as water resistance strength.

<Inorganic fiber product manufacturing method>
The manufacturing method of the inorganic fiber of this invention has the process of making the binder of this invention adhere to an inorganic fiber product, and shape | molding and obtaining an inorganic fiber product. When the binder of the present invention is a kit including the first agent and the second agent, the first agent and the second agent may be attached simultaneously to the inorganic fibers, or may be attached separately.
The manufacturing method of the inorganic fiber product of the present invention is not particularly limited except that the binder of the present invention is used as a binder, and a known method conventionally used for manufacturing inorganic fiber products can be used. As an example, a process of attaching the binder of the present invention to inorganic fibers (hereinafter referred to as an adhesion process), collecting the inorganic fibers with the binder attached thereto, and forming an aggregate having a shape corresponding to the inorganic fiber product to be manufactured. Then, an inorganic fiber product is obtained by performing sequentially the process (henceforth a formation process) of heating the said integration body and hardening the said binder. Hereinafter, each process will be described in more detail.

[Adhesion process]
The inorganic fiber is not particularly limited, and examples thereof include glass wool, rock wool, and ceramic fiber. These may be used alone or in combination of two or more.
The fiber length and fiber diameter of the inorganic fiber may be appropriately set according to the inorganic fiber product to be manufactured, and are not particularly limited. Usually, those having a fiber diameter in the range of 3 to 10 μm are used.
A commercially available thing may be used for an inorganic fiber, and what was manufactured by the well-known method may be used as it is. Inorganic fibers are generally produced by fiberizing raw materials (waste glass, basalt, iron furnace slag, etc.), and examples of the fiberizing method include a flame method and a centrifugal method. The fiberization by these various methods can be performed using a corresponding fiberizing apparatus.

As a method of attaching the binder to the inorganic fiber, for example, a method of spraying the binder on the inorganic fiber using a spray device or the like, after blending the first agent and the second agent using a line mixer or the like in the binder pipe , A method of spraying using a spray device, etc., a method of spraying the first agent and the second agent separately (using a plurality of spray devices, etc.), a method of impregnating inorganic fibers in a binder, an inorganic fiber as a first agent, Examples include a method of impregnating the second agent separately, and any method may be used.
The amount of the binder to be attached to the inorganic fiber is not particularly limited, but is usually in the range of 0.5 to 20% by mass as the nonvolatile content of the binder with respect to the inorganic fiber (100% by mass). The amount of the binder affects the physical properties (such as mechanical strength) of the resulting inorganic fiber product. For example, the greater the binder amount, the higher the mechanical strength of the inorganic fiber product.

[Molding process]
Next, the inorganic fibers to which the binder is attached are accumulated to form an aggregate having a shape corresponding to the inorganic fiber product to be manufactured, and then the aggregate is heated to perform a molding step for curing the binder.
The molding step can be performed by a known method. For example, in the case of producing a plate-like product as an inorganic fiber product, for example, inorganic fibers are deposited on a conveyor, and this deposit is pressed from the up and down direction of the conveyor to be compressed into an aggregate. Is sent to a heating furnace (curing furnace) and heated to cure the binder, whereby a plate-like molded product is obtained.
The amount of inorganic fibers used (the amount of inorganic fibers deposited on the conveyor) and the compression conditions are set according to the thickness, bulk density, etc. of the inorganic fiber product to be manufactured.
The heating conditions (heating temperature, heating time) of the aggregate are not particularly limited as long as the binder in the aggregate is cured, but the heating temperature is preferably in the range of 200 to 270 ° C. If it is lower than 200 ° C., curing may be insufficient and mechanical strength may be insufficient. When it exceeds 270 ° C., the binder may be decomposed, and the yield and the mechanical strength may be lowered. The heating time varies depending on the size of the aggregate, the heating temperature, and the like, and is not particularly limited.

After cooling, a formaldehyde scavenger may be added when the resulting molded product is cooled. Thereby, the amount of formaldehyde emission from the obtained inorganic fiber product can be further reduced. However, when the binder of the present invention contains a formaldehyde scavenger, the same effect can be obtained without addition after heating.
As the formaldehyde scavenger, for example, a known formaldehyde scavenger as described in JP-A No. 2001-178805 can be used.
Examples of the method of adding the formaldehyde scavenger to the molded product include a method of spraying, impregnating or coating an aqueous solution of the formaldehyde scavenger, a method of spraying powder of the formaldehyde scavenger as an aerosol, and the like.
When the formaldehyde scavenger is added, in order to obtain the effect of adding the formaldehyde scavenger sufficiently, the amount of the phenol resin non-volatile content as the total amount of the formaldehyde scavenger optionally contained in the binder of the present invention is sufficient. On the other hand, 0.1 mass% or more is preferable and 0.5 mass% or more is more preferable. Although the upper limit is not particularly limited, in the present invention, it is possible to obtain an inorganic fiber product having a sufficiently small formaldehyde emission amount without adding a formaldehyde scavenger, and the cost is increased even if it is added excessively. From the point etc., 50 mass% or less is preferable with respect to the non volatile matter of a phenol resin, and 25 mass% or less is more preferable.

The obtained molded product may be used as it is as an inorganic fiber product, and may be further subjected to processing such as cutting and packing with a skin material as necessary.
The inorganic fiber product produced by the present invention can be used as, for example, a heat insulating material, a sound absorbing material, and other various molded products (automobile roof, bonnet liner, etc.).

EXAMPLES The present invention will be described in more detail with reference to examples below, but the present invention is not limited to the examples.
In the following examples, “part” and “%” represent “part by mass” and “% by mass”, respectively, unless otherwise specified.

<Synthesis of phenolic resin>
[Synthesis Example 1: Synthesis of phenol resin A (y = 2.3)]
A reactor equipped with a condenser, a thermometer, and a stirrer was charged with 700 parts by mass of phenol, 1026.6 parts by mass of 50% aqueous formaldehyde solution, and 56 parts by mass of 50% aqueous sodium hydroxide solution, and reacted at 65 ° C. for 270 minutes. Then, it cooled to 45 degreeC. After cooling, boric acid was added to neutralize to pH 7.3, neutralized, and adjusted water was added so that the non-volatile content was 50% to obtain phenol resin A.
The molar ratio (value of y) of formaldehyde / phenol [F / P] at the time of synthesis of phenol resin A is 2.3, and the properties of the obtained resin are number average molecular weight = 287, free phenol 2.5% The free formaldehyde was 3.6%. Each of these characteristic values is a value measured by the following procedure.
Number average molecular weight: measured by GPC (polystyrene conversion).
Nonvolatile content: Measured according to 5.6 of JIS K6910.
pH: Measured according to 5.4 of JIS K6910.
Free phenol: Measured according to 5.16 of JIS K6910.
Free formaldehyde: Measured according to 5.17 of JIS K6910.

[Synthesis Examples 2 to 18: Synthesis of phenol resins B to R]
Phenol resins B to R were obtained in the same manner as in Synthesis Example 1 except that the reaction conditions were changed as shown in Tables 1 and 2.
The characteristic values of the obtained phenol resins B to R were measured in the same manner as in Synthesis Example 1. The results are summarized in Tables 1 and 2.

[Synthesis Example 19: Synthesis of phenol resin S]
A reactor equipped with a condenser, a thermometer, and a stirrer was charged with 300 parts of phenol, 650 parts of a 50% aqueous formaldehyde solution, and 51 parts of barium hydroxide octahydrate, and reacted at 60 ° C. for 300 minutes. Cooled to. After cooling, 30% sulfuric acid was added to neutralize to pH 7.3, and then adjusted water was added so that the non-volatile content was 50% to obtain a phenol resin S.
The molar ratio (value of y) of formaldehyde / phenol [F / P] at the time of synthesis of the phenol resin S is 3.4, and the characteristics of the obtained resin are number average molecular weight = 220, free phenol = 0.8 %, Free formaldehyde = 9.0%. These characteristic values were measured in the same procedure as in Synthesis Example 1.

<Binder preparation 1>
[ Reference Example 1 , Examples 2-4, Reference Examples 6-7, Examples 8-18, Reference Examples 19-20, Examples 21-26, Comparative Examples 1-19, Reference Examples ae]
The phenol resin and saccharide synthesized above were mixed so as to have binder compositions shown in Tables 3 and 4 to prepare a binder (non-volatile content: 50% by mass).

[Example 27, Comparative Examples 20-22]
The phenol resin and saccharide synthesized above were mixed at a mass ratio shown in Tables 3 and 4 to obtain a binder (non-volatile content 50%).
Thereafter, this binder (non-volatile content 50%) and 50% urea aqueous solution are mixed at a mass ratio shown in Tables 3 and 4 and reacted at 30 ° C. for 2 hours to prepare a urea-modified binder (non-volatile content 50%). did.

In each of the above examples, a phenol resin, a saccharide, and urea each having a nonvolatile content (solid content) of 50% by mass were used.
The compounding amounts shown in the binder compositions in Tables 3 and 4 indicate the compounding amounts as the nonvolatile components of the respective components, and the ratio of these compounding amounts is the ratio of each component in the nonvolatile components of the binder.
In Tables 3 and 4, the total non-volatile content of the binder composition is 100 parts by mass, and therefore, the amount [parts by mass] of the saccharide is equal to the value of x (% by mass).
Among the components shown in Tables 3 and 4, the sugar “75FG” is an aqueous saccharide solution having a saccharide concentration of 75%, which was used after diluting the saccharide concentration from 75% to 50% with water. . The sugar composition of 75FG (in terms of anhydride) is 42% fructose, 50% glucose, and 8% other sugars. Of the components shown in the binder composition of Table 4, the carbohydrate “HF-55” is a 75% carbohydrate aqueous solution manufactured by Gunei Chemical Industry Co., Ltd. Used by diluting from 75% to 50%. The sugar composition of HF-55 (in terms of anhydride) is 55% fructose, with the balance being glucose as the main component.

[ Reference Example 28]
Phenol resin B (non-volatile content: 50%) synthesized above is used as the first agent, and an aqueous carbohydrate solution obtained by diluting the 75FG with water to a sugar concentration of 50% is used as the second agent. A binder consisting of 20 parts was obtained. The binder composition of Reference Example 28 shown in Table 4 is a mass ratio between the phenol resin (nonvolatile content) in the first agent and the saccharide (nonvolatile content) in the second agent.

<Evaluation>
[Free phenol]
Binders obtained in Reference Example 1 , Examples 2 to 4, Reference Examples 6 to 7, Examples 8 to 18, Reference Examples 19 to 20, Examples 21 to 27, Comparative Examples 1 to 22, and Reference Examples a to e The free phenol was measured according to 5.16 of JIS K6910.
For Reference Example 28, the theoretical value was calculated from the free phenol value (2.1) of phenol resin B and the phenol resin content (80/100) (2.1 × 0.8≈1.7).

[Normal strength and water resistance of molded products]
Using the obtained binder and shirasu balloon (hollow glassy sphere having an average particle diameter of 300 μm), the normal strength and water resistance strength of the molded product were evaluated in the following procedure. The Shirasu balloon is used as a substitute for inorganic fibers for easy evaluation, and is presumed to show the same tendency as the result when inorganic fibers such as glass wool are used.
Shirasu balloon 65g, Reference Example 1 , Examples 2-4, Reference Examples 6-7, Examples 8-18, Reference Examples 19-20, Examples 21-27, Comparative Examples 1-22, Reference Examples ae After uniformly mixing with 23 g of the binder, it was uniformly filled into a mold having a predetermined size (100 mm × 220 mm × 13 mm) and heated at 200 ° C. for 30 minutes to give a molded product (bulk density: 0.26 g / cm ^3). ) In addition, 65 g of Shirasu balloon, 18.4 g of the first agent of the binder of Reference Example 28, and 4.6 g of the second agent were mixed uniformly, and then placed in a mold having a predetermined size (100 mm × 220 mm × 13 mm). Filled uniformly and heated at 200 ° C. for 30 minutes to obtain a molded product (bulk density: 0.26 g / cm ³ ).
Ten test pieces of 100 mm × 20 mm × 13 mm were cut out from the obtained molded product, and normal strength (kgf / cm ² ) was measured using five of them, and water resistance strength (kgf was measured using the remaining five. / Cm ² ) was measured. Specifically, the strength of the five test pieces was measured as it was, and the average value thereof was defined as the normal strength. Moreover, about 5 test pieces, after performing the immersion process for 2 hours in 60 degreeC warm water, intensity | strength measurement was performed and those average values were made into the water-resistant strength.
The strength measurement (normal strength measurement, water resistance strength measurement) was performed under the conditions of a span of 50 mm and a load speed of 10 mm / min by a three-point bending test method according to 5.17 of JIS K6911.

[Formaldehyde emission rate]
In accordance with a conventional method for producing an inorganic fiber-based heat insulating material, an inorganic fiber-based heat insulating material was prepared using the obtained binder.
As production conditions, Reference Example 1 , Examples 2 to 4, Reference Examples 6 to 7, Examples 8 to 18, Reference Examples 19 to 20, Examples 21 to 27, Comparative Examples 1 to 22, Reference Examples a to e. The binder was sprayed so that the coating amount was 2.0 parts by mass with respect to 100 parts by mass of the inorganic fiber, and heated for 150 seconds in a hot-air passing oven at a heating temperature of 230 ° C. At this time, it was molded so as to have a thickness of 50 mm and a density of 30 kg / m ³ to obtain an inorganic fiber heat insulating material.
Moreover, the first agent and the second agent of the binder of Reference Example 28 (first agent: second agent = 80: 20) were individually spray nozzles, and their total coating amount was 100 parts by mass of inorganic fibers. On the other hand, it sprayed so that it might become 2.0 mass parts, and it heated for 150 second in the hot air passage type oven with a heating temperature of 230 degreeC. At this time, it was molded so as to have a thickness of 50 mm and a density of 30 kg / m ³ to obtain an inorganic fiber heat insulating material.
As the inorganic fiber, glass fiber obtained by a centrifugal method was used.
The formaldehyde emission rate of the inorganic fiber heat insulating material produced as described above was measured according to the formaldehyde emission rate measurement method of JIS A1901.

Said evaluation result was written together in Tables 3-4.
In addition, in FIG. 1, lines of y = −25 / (x + 10) +3.8, y = −0.012x + 1.9 and x = 90, Reference Example 1 , Examples 2 to 4, Reference Examples 6 to 7, The coordinates (x, y) of Examples 8 to 18, Reference Examples 19 to 20, Examples 21 to 28, and Comparative Examples 1 to 22 were plotted (horizontal axis: x, vertical axis: y). In FIG. 1, ◯ indicates the coordinates of the example and the coordinates of the reference example, and the numerical values attached to ◯ indicate the example number and the reference example number . X shows the coordinate of a comparative example, and the numerical value attached | subjected to x shows a comparative example number.
As shown in these results, the values of x and y satisfy Equations 1 to 3 (y = −25 / (x + 10) +3.8, y = −0.012x + 1.9, and x = 90 surrounded by lines) Reference Example 1 , Examples 2 to 4, Reference Examples 6 to 7, Examples 8 to 18, Reference Examples 19 to 20, and Examples 21 to 23 all have a formaldehyde emission rate of 5 μg / m ^2. The amount of free phenol was also 5% or less. Moreover, the strength (normal strength, water resistance strength) of the obtained molded product was also good.
Also in Examples 24-26 using glucose, fructose, or dextrin instead of 75FG as the sugar, Example 27 using urea-modified phenol resin, and Reference Example 28 in which the phenol resin and sugar were separately sprayed The same results as Reference Example 1 , Examples 2 to 4, Reference Examples 6 to 7, Examples 8 to 18, Reference Examples 19 to 20, and Examples 21 to 23 were obtained.
On the other hand, Comparative Examples 1-12 which do not satisfy Formula 1 had many formaldehyde emission rates.
Of Comparative Examples 13 to 15 that do not satisfy Formulas 1 and 2, Comparative Examples 13 to 14 have a high formaldehyde emission rate, free phenol exceeds 5%, and problems such as odor generation and yield reduction due to volatilization of free phenol occur. occured. In Comparative Example 15, free phenol exceeded 5%, and problems such as odor generation and yield reduction due to volatilization of free phenol occurred.
In Comparative Examples 16 to 19 that do not satisfy Formula 2, the free phenol exceeded 5%, and problems such as generation of odor due to volatilization of free phenol, reduction in yield occurred.
Comparative Example 20, which is a urea-modified phenolic resin, corresponds to a currently widely used binder, but the formaldehyde emission rate was significantly higher than that of Comparative Example 10 having the same composition except that it was not urea-modified. Moreover, in Comparative Examples 21 to 22 in which the amount of urea is further increased, the formaldehyde emission rate and the strength of the molded product are greatly reduced in proportion to the amount of urea. In particular, in Comparative Example 22 in which 70 parts by mass is compounded, molding is performed. Could not be made.

In addition, from the results of Reference Examples a to e using a phenol resin using barium hydroxide as the alkali catalyst, even when barium hydroxide is used as the alkali catalyst, the strength of the molded product is sufficiently increased by the addition of saccharides. It was confirmed that the formaldehyde emission rate could be reduced while maintaining. However, in all of Reference Examples a to d, the value of y was 3.4 and did not satisfy Formula 1, but the formaldehyde emission rate was reduced to 5 μg / m ² · h. This is considered because the preferable ranges of x and y differ depending on the alkali catalyst used.

Claims (5)

Contains phenolic resin and sugar,
The phenol resin is obtained by reacting phenols and aldehydes containing formaldehydes in the presence of sodium hydroxide,
The ratio x (mass%) of the saccharide to the total amount of the nonvolatile content of the phenol resin and the saccharide, and the molar ratio (aldehydes / phenols) y of the phenols and the aldehydes are represented by the following formula 1. A binder for producing inorganic fiber products satisfying ~ 3.
Formula 1: y ≦ −25 / (x + 10) +3.8
Formula 2: y ≧ −0.012x + 1.9
Formula 3: 30 ≦ x ≦ 90 A first agent containing a phenolic resin and a second agent containing a saccharide,
The phenol resin is obtained by reacting phenols and aldehydes containing formaldehydes in the presence of sodium hydroxide,
The ratio x (mass%) of the saccharide to the total amount of the nonvolatile content of the phenol resin and the saccharide, and the molar ratio (aldehydes / phenols) y of the phenols and the aldehydes are represented by the following formula 1. A binder for producing inorganic fiber products satisfying ~ 3.
Formula 1: y ≦ −25 / (x + 10) +3.8
Formula 2: y ≧ −0.012x + 1.9
Formula 3: 30 ≦ x ≦ 90 A step of reacting a phenol with an aldehyde containing formaldehyde in the presence of sodium hydroxide to obtain a phenol resin;
Mixing the phenolic resin and sugar to obtain a binder for producing inorganic fiber products ,
The ratio x (mass%) of the saccharide to the total amount of the nonvolatile content of the phenol resin and the saccharide, and the molar ratio (aldehydes / phenols) y of the phenols and the aldehydes are represented by the following formula 1. The manufacturing method of the binder for inorganic fiber products manufacture which satisfy | fills ~ 3 .
Formula 1: y ≦ −25 / (x + 10) +3.8
Formula 2: y ≧ −0.012x + 1.9
Formula 3: 30 ≦ x ≦ 90   The manufacturing method of an inorganic fiber product which has the process of making the inorganic fiber product binder of Claim 1 adhere to an inorganic fiber, and shape | molding and obtaining an inorganic fiber product.   The inorganic fiber product which has the process of making it adhere to the inorganic fiber after mixing the 1st agent and 2nd agent of the binder for inorganic fiber product manufacture of Claim 2 after it mixes, or shape | molding, and obtaining an inorganic fiber product Manufacturing method.

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