JP2019173235A - Binder for inorganic fiber product and manufacturing method therefor, manufacturing method of inorganic fiber product - Google Patents

Abstract

To provide a binder for inorganic fiber product capable of manufacturing an inorganic fiber product excellent in water dilution property, having reduced formaldehyde emission amount, having sufficient strength, and excellent in appearance, a manufacturing method of the binder for inorganic fiber product, and a manufacturing method of the inorganic fiber product using the binder for inorganic fiber product.SOLUTION: There is provided a binder for inorganic fiber product containing a resol type phenol resin, and amino acid, with content of the amino acid of 0.5 to 33 pts.mass based on 100 pts.mass of a resin solid component of the resol type phenol resin. There is provided a manufacturing method of the binder for inorganic fiber product including adding monoamine to the resol type phenol resin at less than 60°C. There is provided a manufacturing method of the inorganic fiber product for adhering the binder for inorganic fiber product to the inorganic fiber and molding the inorganic fiber to obtain the inorganic fiber product.SELECTED DRAWING: None

Description

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

Conventionally, inorganic fiber products formed by bonding inorganic fibers such as glass wool, rock wool, or ceramic fibers with a binder are used as heat insulating materials, sound absorbing materials, or other various molded products (automobile roofs, bonnet liners, etc.). It is used.
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 formaldehyde (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 formaldehyde is volatilized in the manufacturing process and formaldehyde is diffused from the resulting inorganic fiber product. Formaldehyde is a substance that adversely affects the human body. For example, aldehyde 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 Standard Law, which regulates the amount of formaldehyde emitted, was enforced in 2003. Under the revised Building Standards Law, the formaldehyde emission rate of 5 μg / m ² · hr or less as measured by JIS A1901 is not regulated, so the formaldehyde emission rate is 5 μg even for inorganic fiber products. / M ² · hr or less is desired.

As one of countermeasures for the problem of formaldehyde volatilization in the manufacturing process of inorganic fiber products (when the binder is sprayed, etc.), phenol resin is modified with urea. In this case, free formaldehyde in the phenol resin is captured by the urea introduced into the phenol resin, the amount of formaldehyde volatilization during the manufacturing process is reduced, and the working environment is improved.
As a countermeasure against the problem of formaldehyde being diffused from inorganic fiber products, it is now common to use a formaldehyde scavenger such as ethylene urea or adipic acid dihydrazide (see, for example, Patent Document 1). The formaldehyde scavenger reacts with the generated formaldehyde and immobilizes it to reduce formaldehyde emission.
However, in the conventional method, it is difficult to produce an inorganic fiber product with low formaldehyde emission and good performance at low cost.

  For example, although a method of modifying a phenol resin with urea is effective in reducing the amount of formaldehyde volatilized in the production process, the amount of formaldehyde emitted 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.

Moreover, although the use of formaldehyde scavengers is effective in reducing the amount of formaldehyde emitted, conventional formaldehyde scavengers are more expensive than phenolic resins. In addition, when trying to obtain an inorganic fiber product having a formaldehyde emission rate of 5 μg / m ² · hr or less, the amount of formaldehyde scavenger used 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, there is a need for a phenolic resin binder that can obtain an inorganic fiber product having a formaldehyde emission rate of 5 μg / m ² · hr or less without using the formaldehyde scavenger in combination.

  Under such circumstances, as one of countermeasures for the problem that formaldehyde is volatilized in the manufacturing process of inorganic fiber products in recent years, glycine is obtained at 60 to 75 ° C. after reacting formaldehyde with phenol to obtain a resol type phenol resin. Has been proposed in which unreacted formaldehyde and phenol are reacted with glycine to form a condensate (Patent Documents 2 and 3). In addition, as a method for reducing formaldehyde emission, a binder for inorganic fiber products in which sugar is added to a resol type phenol resin is also known (Patent Documents 4 and 5).

JP 2001-178805 A JP-A-2006-180115 Special table 2013-536311 gazette JP 2014-148422 A Japanese Patent No. 5328988

  As in Patent Documents 2 and 3, when the unreacted formaldehyde and phenol are reacted with glycine to form a condensate, the water-dilutability of the binder for inorganic fiber products is deteriorated. Therefore, it becomes difficult to adhere the binder for inorganic fiber products to inorganic fiber. Moreover, although the binder for inorganic fiber products like patent documents 4 and 5 is excellent in water reducibility, since the color of the manufactured inorganic fiber product turns into a tea system color and differs from the conventional color, some There are cases in which it is pointed out by the customer that the appearance is not preferable. In addition, a high-density board product may cause a decrease in strength, such as an increase in the amount of deflection, as compared with a product using an existing phenol resin.

  The present invention provides an inorganic fiber product binder that is excellent in water dilutability, has reduced formaldehyde emission, has sufficient strength, and has an excellent appearance, and a method for producing the inorganic fiber product binder Another object is to provide a method for producing an inorganic fiber product using the inorganic fiber product binder.

The present invention has the following aspects.
[1] A binder for inorganic fiber products comprising a resol type phenolic resin and an amino acid.
[2] The binder for inorganic fiber products according to [1], wherein the content of the amino acid is 0.5 to 33 parts by mass with respect to 100 parts by mass of the resin solid content of the resol type phenol resin.
[3] The binder for inorganic fiber products according to [1] or [2], wherein the pH is 6.0 to 13.0.
[4] A method for producing an inorganic fiber product, wherein the inorganic fiber product is obtained by attaching the inorganic fiber product binder according to any one of [1] to [3] to the inorganic fiber and molding the inorganic fiber.
[5] A method for producing a binder for inorganic fiber products, wherein an amino acid is added to a resol-type phenolic resin at less than 60 ° C.
[6] The method for producing a binder for inorganic fiber products according to [3], wherein the addition amount of the amino acid is 0.5 to 33 parts by mass with respect to 100 parts by mass of the resin solid content of the resol type phenol resin. .

  ADVANTAGE OF THE INVENTION According to this invention, the amount for formaldehyde emission is reduced with the binder for inorganic fiber products excellent in water reducibility, An inorganic fiber product which has sufficient intensity | strength and was excellent in the external appearance can be manufactured.

Regarding the binders A-1 to A-7, A-9, and A-13 for inorganic fiber products of Examples 1 to 7 and Comparative Examples 1 and 5, the added amount of glycine is taken on the horizontal axis, and the normal strength is taken on the vertical axis. It is a graph. For the binders A-1 to A-7, A-9, and A-13 for inorganic fiber products of Examples 1 to 7 and Comparative Examples 1 and 5, the horizontal axis represents the amount of glycine added, and the vertical axis represents moisture resistance. It is a graph. For binders B-1 to B-7, B-9, and A-13 for inorganic fiber products of Examples 1 to 7 and Comparative Examples 1 and 5, the amount of glycine added is on the horizontal axis and the amount of diffused F is on the vertical axis. It is a graph taken. For the binders B-1 to B-7, B-9, and A-13 for inorganic fiber products of Examples 1 to 7 and Comparative Examples 1 and 5, the tensile strength (normal strength, moisture resistance) with the added amount of glycine as the horizontal axis It is the graph which took intensity | strength) on the vertical axis | shaft.

[Binder for inorganic fiber products]
The binder for inorganic fiber products of the present invention (hereinafter also referred to as “the present binder”) is a binder for binding inorganic fibers such as glass wool, rock wool, and ceramic fibers in inorganic fiber products. This binder contains a resol type phenol resin and an amino acid.
The binder may further contain other components other than the resol type phenolic resin and the amino acid as long as the effects of the present invention are not impaired, if necessary.

(Resol type phenol resin)
The resol type phenol resin is a reaction product of a phenol and an aldehyde in the presence of an alkali catalyst.
When phenols and aldehydes are reacted in the presence of an alkali catalyst, an addition reaction in which aldehydes are added to the aromatic ring of phenols occurs, and then polymerizes through a condensation reaction.

  Phenols are compounds having an aromatic ring and a hydroxyl group bonded to the aromatic ring. Examples of phenols include phenol, alkylphenols (o, m, p cresol, o, m, p ethylphenol, xylenol isomers, etc.), polyaromatic phenols (α, β Naphthol, etc.), polyhydric phenols (bisphenol A, bisphenol F, bisphenol S, pyrogallol, resorcin, catechol, hydroquinone, etc.). These phenols may be used individually by 1 type, and may use 2 or more types together. Among these, practical substances are phenol, cresols of o, m, and p, isomers of xylenol, resorcin, and catechol.

  Aldehydes are at least one compound selected from the group consisting of compounds having a formyl group and multimers thereof. Examples of aldehydes include formaldehyde, paraformaldehyde, acetaldehyde, propyl aldehyde, benzaldehyde, salicylaldehyde, glyoxal, and the like. These aldehydes may be used individually by 1 type, and may use 2 or more types together. Among these, practical substances are formaldehyde and paraformaldehyde.

The weight average molecular weight of the resol type phenol resin is preferably 800 or less, more preferably 600 or less, and still more preferably 400 or less, from the viewpoint of water dilution and stability over time. When the weight average molecular weight of the resol type phenol resin is less than 150, there is a possibility that the yield of the binder in the inorganic fiber product may be reduced or the strength may be reduced.
The weight average molecular weight of the resol type phenol resin is a value measured by gel permeation chromatography (GPC) using polystyrene as a standard substance.

The resol type phenol resin is preferably liquid.
The resin solid content of the resol type phenol resin is preferably 30% by mass or more, and more preferably 40% by mass or more from the viewpoint of transportation cost.
The “resin solid content” of the resol type phenol resin refers to the non-volatile content of the resol type phenol resin. The nonvolatile content indicates a value measured according to JIS K6910 5.6.

(amino acid)
The amino acid is not particularly limited, and examples thereof include glycine, glutamic acid, glutamine, cysteine, alanine, arginine, asparagine, aspartic acid, sarcosine, serine, threonine, valine, leucine, isoleucine, lysine and methionine. As the amino acid, glycine and glutamic acid are preferable because an effect of reducing the amount of formaldehyde diffused is easily obtained.
An amino acid may be used individually by 1 type, and may use 2 or more types together.

The content of the amino acid in the binder is preferably 0.5 to 33 parts by mass and more preferably 5 to 15 parts by mass with respect to 100 parts by mass of the resin solid content of the resol type phenol resin. When the amino acid content is at least the lower limit of the above range, the amount of formaldehyde released is sufficiently reduced, and an inorganic fiber product having high normal strength and high moisture resistance is easily obtained. If the amino acid content is not more than the upper limit of the above range, the economy is excellent.
In addition, normal strength shows mechanical strength (tensile strength, bending strength, etc.) in a dry state. The moisture resistance indicates the mechanical strength in a wet state.

(Other ingredients)
As other components, it can be used by appropriately selecting from known components that can be blended in the binder. Examples thereof include urea, ethylene urea, resorcin, melamine, dicyandiamide, ammonia, a curing accelerator, a silane coupling agent, a known formaldehyde scavenger, a water repellent, a dust prevention oil, and water. Other components may be used alone or in combination of two or more.

By including at least one selected from urea, melamine, ethylene urea, resorcin, and dicyandiamide (DCDA) as the binder for the heat insulating material, the amount of formaldehyde emitted can be further reduced.
When the binder for heat insulating materials contains urea, 5-100 mass parts is preferable with respect to 100 mass parts of resin solid content of a resol type phenol resin, and, as for content of urea, 10-70 mass parts is more preferable. The preferable range of the content of melamine, ethylene urea, resorcin, and DCDA is the same as the preferable range of the urea content.

When this binder contains ammonia, it reacts with the free formaldehyde in this binder and converts to hexamine, thereby improving the working environment. Moreover, by mix | blending ammonia, pH of this binder increases and water dilutability improves. The improvement of water dilutability is preferable from the viewpoint of preventing adhesion of the binder to the piping and clogging of the spray nozzle.
As for the compounding quantity of ammonia, 0-20 mass% is preferable with respect to the resin solid content of a phenol resin.

The binder may further contain a curing accelerator.
Examples of the curing accelerator include ammonium salts such as ammonium sulfate, ammonium chloride, and ammonium phosphate.
As for content of the hardening accelerator in this binder, 0-10 mass parts is preferable with respect to 100 mass parts of resin solid content of a resol type phenol resin, and 3-5 mass parts is more preferable.

When this binder contains a silane coupling agent, the water resistance and mechanical strength of the inorganic fiber product are improved.
The silane coupling agent is not particularly limited, and examples thereof include aminosilane compounds such as N-2- (aminoethyl) -3-aminopropylmethyldimethoxysilane and 3-aminopropyltriethoxysilane.
As for content of the silane coupling agent in this binder, 0-1 mass part is preferable with respect to 100 mass parts of resin solid content of a resol type phenol resin.

Examples of the formaldehyde scavenger include formaldehyde scavengers described in JP-A No. 2001-178805.
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.

The pH of the binder is preferably 6.0 to 13.0, more preferably 6.3 to 11.0, further preferably 6.5 to 9.0, particularly preferably 6.5 to 8.0, 6 .5 to 7.0 is even more preferable. If pH is more than the lower limit of the said range, an installation will not be damaged. Moreover, the solubility in water becomes better.
If pH is below the upper limit of the said range, it is economical from the point of usage-amounts, such as a catalyst and an additive. The pH is a value at 25 ° C.

[Method for producing binder for inorganic fiber product]
This binder is obtained by adding an amino acid to a resol type phenol resin at less than 60 ° C. For example, there is a method in which phenols and aldehydes are reacted in the presence of an alkali catalyst to obtain a resol type phenol resin, and then an amino acid is added at less than 60 ° C.

  The reaction between phenols and aldehydes can be performed by a known method. For example, a method of charging a reaction vessel having a stirrer, a reflux device and a temperature control mechanism with phenols, aldehydes, an alkali catalyst, water and the like and maintaining an arbitrary reaction time at an arbitrary reaction temperature can be mentioned. After the start of the reaction, an additional alkali catalyst and optional additives may be added as necessary.

  The molar ratio of aldehydes to phenols (aldehydes / phenols) is preferably 1.0 to 4.0, and more preferably 1.5 to 2.5. If the molar ratio of aldehydes to phenols is not less than the lower limit of the above range, it is easy to suppress odor generation or yield reduction due to volatilization of unreacted phenols. If the molar ratio of aldehydes to phenols is below the upper limit of the above range, a large amount of unreacted aldehydes will not remain, formaldehyde will not volatilize in the working environment atmosphere during the manufacturing process, and Does not harm health. Moreover, the amount of aldehydes emitted from the inorganic fiber product obtained using the binder is reduced.

  The alkali catalyst is not particularly limited as long as the reaction between phenols and aldehydes can proceed, and various alkaline substances can be used. Specific examples include hydroxides of alkali metals such as sodium and potassium (sodium hydroxide and potassium hydroxide), and alkaline earth metal hydroxides such as calcium, magnesium and barium (calcium hydroxide and magnesium hydroxide). Inorganic alkaline substances such as sodium carbonate and ammonia; tertiary amines such as triethylamine, trimethylamine and triethanolamine; DBU (1,8-diazabicyclo [5.4.0] undec-7-ene ), Organic alkaline substances such as cyclic amines such as DBN (1,5-diazabicyclo [4.3.0] non-5-ene); Usually, when an alkaline earth metal is used, the water dilutability and stability over time of the resin are lower than when an alkali metal is used, but the water resistance is improved. This is because alkaline earth metals and their salts are less soluble in water than alkali metals. These alkali catalysts may be used individually by 1 type, and may use 2 or more types together.

  As for the usage-amount of an alkali catalyst, 1-30 mass parts is preferable with respect to 100 mass parts of phenols. If the usage-amount of an alkali catalyst is more than the lower limit of the said range, reaction will fully advance. If the usage-amount of an alkali catalyst is below the upper limit of the said range, control of reaction will be easy.

50-90 degreeC is preferable and, as for the reaction temperature of reaction of phenols and aldehydes, 60-80 degreeC is more preferable. If the reaction temperature is at least the lower limit of the above range, a sufficient reaction rate can be obtained. If reaction temperature is below the upper limit of the said range, control of reaction will be easy.
The reaction time can be, for example, 2 to 8 hours.

After reacting phenols and aldehydes at a reaction temperature within the above range, the amino acid is added after adjusting the temperature of the resol-type phenol resin to be less than 60 ° C. By adding an amino acid at a temperature lower than 60 ° C., it is possible to suppress the formation of a condensate by reacting the free phenol and free formaldehyde with the amino acid contained in the resol type phenol resin. Thereby, it is suppressed that the water dilution property of this binder obtained falls.
The free phenols are unreacted phenols measured according to JIS K6910 5.16. Free aldehydes are unreacted aldehydes measured according to 5.17 of JIS K6910.

  The temperature of the resol type phenol resin when adding an amino acid is less than 60 ° C, preferably 10 to 50 ° C, more preferably 15 to 40 ° C, and particularly preferably 20 to 35 ° C. If the temperature of the resol type phenol resin at the time of amino acid addition is below the upper limit of the said range, this binder excellent in water reducibility will be easy to be obtained. If the temperature of the resol-type phenol resin at the time of amino acid addition is equal to or higher than the lower limit of the above range, the amine is easily dissolved in the resin, the heat of solution at the time of amine addition is relaxed, and temperature control can be facilitated.

  0.5-33 mass parts is preferable with respect to 100 mass parts of resin solid content of a resol type phenol resin, and, as for the addition amount of an amino acid, 5-15 mass parts is more preferable. If the amount of amino acid added is within the above range, the amount of formaldehyde emitted from the inorganic fiber product can be sufficiently reduced, and the present binder excellent in water dilution can be easily obtained.

In the present invention, after reacting phenols and aldehydes in the presence of an alkali catalyst, or after adding an amino acid, neutralization with an acid or dilution with water may be performed as necessary.
Acids used for neutralization include inorganic acids such as boric acid, sulfuric acid, hydrochloric acid, nitric acid, phosphoric acid and sulfamic acid, formic acid, oxalic acid, acetic acid, citric acid, lactic acid, sulfanilic acid, benzoic acid, phenolsulfonic acid, para Organic acids such as toluenesulfonic acid, methanesulfonic acid, lauric acid and the like can be mentioned. An acid may be used individually by 1 type and may use 2 or more types together.

Moreover, in this invention, after making phenols and aldehydes react in presence of an alkali catalyst, or after adding an amino acid, another component is added as needed.
The temperature of the resol-type phenol resin when adding other components is preferably less than 60 ° C, more preferably 10 to 50 ° C, particularly preferably 15 to 40 ° C, and still more preferably 20 to 35 ° C.

In addition, the manufacturing method of the binder for heat insulating materials of this invention is not limited to an above described method. For example, you may add an amino acid to a commercially available resol type phenol resin at less than 60 degreeC.
The temperature of the binder before use is preferably less than 60 ° C, more preferably 10 to 50 ° C, particularly preferably 15 to 40 ° C, and still more preferably 20 to 35 ° C.

  As described above, in the present invention, a binder for an inorganic fiber product including a resol type phenol resin and an amino acid is used. This binder is excellent in water dilutability because it contains an amino acid without reacting with free phenols or aldehydes to form a condensate.

Moreover, when this binder is made to adhere to an inorganic fiber and is baked and cured, free phenols or aldehydes in the binder and an amino acid form a condensate by a Mannich reaction. Since it is thought that this Mannich condensation product captures diffused formaldehyde, the amount of formaldehyde emitted is sufficiently reduced in inorganic fiber products produced using this binder.
In addition, an inorganic fiber product produced using this binder containing an amino acid has a yellow color as in the conventional product, and the normal strength and moisture resistance are improved.
The binder is particularly useful for the production of insulation.

[Production method of inorganic fiber products]
The method for producing an inorganic fiber product of the present invention is a method for obtaining an inorganic fiber product by attaching the binder to the inorganic fiber and molding the inorganic fiber. As needed, you may harden this binder by baking after making this binder adhere to an inorganic fiber.
Examples of the inorganic fiber product manufactured by the manufacturing method of the present invention include a heat insulating material, a sound absorbing material, an automobile roof, a liner such as a bonnet, and the like. The present invention is particularly useful for the production of thermal insulation. The inorganic fiber product manufactured by the manufacturing method of the present invention may be formed of a molded body, or may further include other members other than the molded body such as a skin material for packaging.

  The inorganic fiber is not particularly limited, and examples thereof include glass wool, rock wool, and ceramic fiber. An inorganic fiber may be used individually by 1 type, and may use 2 or more types together.

Examples of the method of attaching the binder to the inorganic fiber include a method of spraying the binder on the inorganic fiber using a spray device and the like, a method of impregnating the inorganic fiber by immersing the binder in the binder, and the like.
Since this binder is excellent in water dilutability, it can be easily and uniformly adhered to inorganic fibers by diluting to an appropriate concentration with water as necessary.

  The adhesion amount of the present binder to the inorganic fiber is not particularly limited, and can be, for example, 0.5 to 20% by mass as the resin solid content of the present binder with respect to the inorganic fiber (100% by mass).

  The inorganic fiber to which the present binder is attached can be molded by a known method. For example, in the case of a plate-like heat insulating material, the inorganic fibers to which the binder is attached are deposited on a conveyor, and the deposit is pressed from the up and down direction of the conveyor to be compressed into an aggregate, which is heated in a heating furnace (cured) A method of curing the binder by sending it to a furnace and baking it.

The baking temperature should just be the temperature range which this binder hardens | cures, and 180-270 degreeC is preferable. If the firing temperature is equal to or higher than the lower limit of the above range, curing of the binder is likely to proceed sufficiently, and the formaldehyde emission amount is likely to be sufficiently reduced. When the firing temperature is equal to or lower than the upper limit of the above range, the present binder is difficult to be decomposed, and a decrease in yield and a decrease in mechanical strength are easily suppressed.
The firing time can be appropriately set depending on the size of the aggregate, the firing temperature, and the like.

EXAMPLES Hereinafter, although an Example demonstrates this invention concretely, this invention is not limited by the following description. In the following description, “part” means “part by mass” unless otherwise specified.
[Example 1]
A reactor equipped with a condenser, a thermometer and a stirrer was charged with 1350 parts of phenol, 1893.7 parts of a 50% aqueous formaldehyde solution and 135 parts of barium hydroxide octahydrate, and reacted at 60 ° C. for 360 minutes. After cooling to 35 ° C., a resol type phenol resin was synthesized. The molar ratio of formaldehyde / phenol [F / P] is 2.2, and the properties of the obtained resin are as follows: weight average molecular weight = 340, free phenol = 5.0 mass%, free formaldehyde = 3.8 mass%. there were.
After adding glycine at a ratio of 0.7 parts to 100 parts by weight of the above-mentioned resol type phenolic resin while suppressing heat of dissolution to 35 ° C. or less, adjusting water is added so that the resin solid content is 50% by mass Binder A-1 for inorganic fiber products was obtained.
Furthermore, 43 parts of urea, 3 parts of ammonium sulfate, 1 part of aminosilane, and 10 parts of 25 mass% aqueous ammonia are mixed with 100 parts of solid content of binder A-1 for inorganic fiber products at 35 ° C. to bind inorganic fiber products. B-1 was obtained.

[Examples 2 to 7]
Except having changed the addition amount of glycine as shown in Table 1, it carried out similarly to Example 1, and prepared binder A-2-A-7 for inorganic fiber products. Furthermore, other components were added to binders A-2 to A-7 for inorganic fiber products in the same manner as in Example 1 to obtain binders B-2 to B-7 for inorganic fiber products.

[Example 8]
A binder A-8 for inorganic fiber products was prepared in the same manner as in Example 1 except that glycine was changed to glutamic acid. Further, other components were added to the inorganic fiber product binder A-8 in the same manner as in Example 1 to obtain an inorganic fiber product binder B-8.

[Comparative Example 1]
A resol type phenolic resin was synthesized in the same manner as in Example 1, and adjusted water was added so that the resin solid content was 50% by mass, which was designated as binder A-9 for inorganic fiber products. Further, other components were added to the inorganic fiber product binder A-9 in the same manner as in Example 1 to obtain an inorganic fiber product binder B-9.

[Comparative Example 2]
A resol type phenolic resin was synthesized in the same manner as in Example 1 and neutralized by adding 30% sulfuric acid to pH 7.3 after cooling to 35 ° C., and then adjusted so that the resin solid content was 50% by mass. What added water was made into binder A-10 for inorganic fiber products. Further, other components were added to the inorganic fiber product binder A-10 in the same manner as in Example 1 to obtain an inorganic fiber product binder B-10.

[Comparative Example 3]
A resol-type phenol resin was synthesized in the same manner as in Example 1, neutralized by adding 30% sulfuric acid so as to have a pH of 7.3 after cooling to 35 ° C., and at a ratio of 30 parts to 100 parts of the resin solid content. Glucose fructose liquid sugar (isomerized sugar, product name: Three Sugar 75FG, solid concentration 75% by mass, manufactured by Gunei Chemical Industry Co., Ltd.) was added, and adjusted water was added so that the resin solid content was 50% by mass. This was designated as binder A-11 for inorganic fiber products. Further, other components were added to the inorganic fiber product binder A-11 in the same manner as in Example 1 to obtain an inorganic fiber product binder B-11.

[Comparative Example 4]
The binder A for inorganic fiber products was the same as in Example 1 except that the temperature of the resol-type phenolic resin when adding glycine was changed to 70 ° C. and free phenol, formaldehyde and glycine were reacted to form a condensate. -12 was obtained. Further, other components were added to the inorganic fiber product binder A-12 in the same manner as in Example 1 to obtain an inorganic fiber product binder B-12.

[Comparative Example 5]
Except having changed the addition amount of glycine as shown in Table 1, it carried out similarly to Example 1, and prepared binder A-13 for inorganic fiber products. Further, other components were added to the inorganic fiber product binder A-13 in the same manner as in Example 1 to obtain an inorganic fiber product binder B-13.

[Water reducibility (miscibility)]
According to the provisions of JIS K6910: 2007, 5.5, water miscibility (mass fraction%) was measured to evaluate water dilutability. In addition, resin solid content was used for the mass of the sample in calculation of miscibility. In the measurement of the miscibility, when no turbidity was observed even when an amount of water corresponding to the miscibility of 4000% was added, the measurement was terminated at that point, and the miscibility was determined to be over 4000%.
In addition, if the miscibility computed using the mass of the resin solid content of a sample is 4000% or more, it can be used without a problem as a binder for inorganic fiber products.

[PH]
The pH of the binder for inorganic fiber products was measured according to JIS K6910: 2007 5.4.

[FP (free phenol content)]
The FP (free phenol amount) of the binder for inorganic fiber products was measured in accordance with 5.16 of JIS K6910: 2007.

[FF (free formaldehyde amount)]
The FF (free formaldehyde amount) of the binder for inorganic fiber products was measured in accordance with 5.17 of JIS K6910: 2007.

[Tensile strength]
After diluting the binder for inorganic fiber products in each example with water so that the concentration of the resin solid content is 35% by mass, the resin solid content is 3% by mass in 25 g of glass beads (average particle size 100 μm). And mixed. The obtained mixture was uniformly filled into a dogbone mold (length 75 mm, minimum width (center in the length direction) 25 mm, maximum width 42 mm, thickness 7 mm), and fired at 190 ° C. for 30 minutes for testing. Pieces were made. A total of 6 test pieces were produced under the same conditions.
Tensile strength (normal strength) was measured using three test pieces, and the remaining three test pieces were measured for tensile strength (humidity resistance) after being left for 24 hours in a thermo-hygrostat at a temperature of 65 ° C. and a humidity of 95%. .
The tensile strength was carried out under the condition of a load speed of 5 mm / min in accordance with 5.18 of JIS K6911: 2006. The tensile strength (N / mm ² ) is calculated by the measurement value (N) / breakage area (25 × 7 = 175 mm ² ), but the break area was constant at 175 (mm ² ), so the measurement value (N) Only compared.

[Formaldehyde emission]
Measurement of formaldehyde emission (amount of emission F) was performed in accordance with 7 of JIS A 1902-4: 2015.
The binder for inorganic fiber products was diluted with water so that the concentration of the resin solid content was 10% by mass, and impregnated into glass filter paper (GA-100 manufactured by ADVANTEC) cut into 15 cm square. The adhesion amount of the binder was about 40% by mass. Subsequently, the glass filter paper to which the binder for inorganic fiber products was made to adhere was baked at 200 degreeC for 10 minute (s). After firing, the center of the filter paper was cut into 5 cm square (surface area 25 cm ² ) and placed in a 1 L capacity plastic container (area of the filter paper surface / poly container volume = 2.2 m ² / m ³ ). An inner lid with a hole was fitted into the opening of a plastic container, a passive sampler for repairing aldehyde / ketone DSD-DNPH (manufactured by Supelco) was inserted, and sealed with a sealing tape. Formaldehyde was collected by allowing to stand at a temperature of 28 ° C. and a humidity of 50% for 24 hours. The formaldehyde repaired with the sampler after collection was extracted with acetonitrile so that the extract became 5 mL. The formaldehyde concentration in the extract was analyzed by high performance liquid chromatograph (HPLC) under the following conditions. Those having an emission F amount of 5 μg / L or less indicate that the emission grade F ☆☆☆☆ is achieved.
(HPLC measurement conditions)
Equipment and model used: PD8020 manufactured by Tosoh Corporation
Column: Inert Sustain C18 3.0 × 150,
Eluent: acetonitrile: water (volume ratio) = 55: 45,
Flow rate: 0.45 mL / min,
Injection volume: 20 μL,
Detector conditions: UV 360 nm.

  The conditions of the binder for inorganic fiber products of each example and various evaluation results are shown in Tables 1, 2 and FIGS.

As shown in Table 1, the binders A-1 to A-8 for inorganic fiber products of Examples 1 to 8, in which an amino acid was added to a resol type phenolic resin at 35 ° C. or lower, formed a condensation product of phenol, formaldehyde and glycine. Compared with the binder A-12 for inorganic fiber products of Comparative Example 4 and the binder A-13 for inorganic fiber products of Comparative Example 5 in which the amount of glycine added was large, water dilution was superior. Moreover, as shown in Table 2 and FIG. 3, the binders B-1 to B-8 for inorganic fiber products to which other components are further added in Examples 1 to 8 are Comparative Examples 1 and 2 in which no amino acid is added. Compared with the binders B-9 and B-10 for thermal insulation, the amount of formaldehyde emitted was reduced. Moreover, in Examples 1-8, the test piece was yellow and the external appearance was favorable.
In addition, as shown in Table 1, Table 2, FIG. 1, FIG. 2, and FIG. There was a tendency that the normal strength and the moisture resistance strength were higher as the amount of added was larger.
In Comparative Example 3 in which an isomerized sugar was added instead of an amino acid, although the amount of diffused formaldehyde was reduced, the normal strength and moisture resistance were low, and the test piece became a brown color.

Claims (6)

  A binder for inorganic fiber products containing a resol type phenolic resin and an amino acid.   The binder for inorganic fiber products of Claim 1 whose content of the said amino acid is 0.5-33 mass parts with respect to 100 mass parts of resin solid content of the said resol type phenol resin.   The binder for inorganic fiber products of Claim 1 or 2 whose pH is 6.0-13.0.   The manufacturing method of an inorganic fiber product which adheres the binder for inorganic fiber products as described in any one of Claims 1-3 to an inorganic fiber, shape | molds the said inorganic fiber, and obtains an inorganic fiber product.   The manufacturing method of the binder for inorganic fiber products which adds an amino acid to a resol type phenol resin at less than 60 degreeC.   The manufacturing method of the binder for inorganic fiber products of Claim 5 whose addition amount of the said amino acid is 0.5-33 mass parts with respect to 100 mass parts of resin solid content of the said resol type phenol resin.

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