JPS6284144A - Highly dustproof powdery phenolic resin composition and its production - Google Patents

Abstract

PURPOSE:To obtain the titled composition capable of keeping workplace environment clean in its production and/or use, enabling working efficiency to be improved and the cost of pollution control equipment to be reduced, by incorporating powdery phenolic resin with specific ester compound and/or oils. CONSTITUTION:The objective composition can be obtained by incorporating (A) 100pts. by wt. of powdery phenolic resin with 0.3-3wt% of (B) at least one kind of liquid ester compound with a boiling point >=200 deg.C selected from phosphoric esters and both aliphatic and aromatic carboxylic acid esters and/or (C) oils. The process is as follows: the component B and/or the component C is mixed, in advance, with a powdery material vivtually incompatible therewith followed by with the component A, then carrying out a cogrinding. Said powdery material is, e.g., hexamethylene-tetramine, calcium carbonate.

Description

DETAILED DESCRIPTION OF THE INVENTION Field of Industrial Application The present invention relates to a powdered phenolic resin composition with excellent dustproof properties useful as a binder for riser heat insulators, building components, molding materials, grindstones, etc., and a method for producing the same. More specifically, the present invention relates to a powdered phenolic resin composition in which a powdered phenolic resin contains a specific amount of a specific ester compound and/or oil as a dusting prevention agent, and a method for producing the same.

PRIOR TECHNOLOGY Conventionally, phenolic resins are miscible with a wide range of materials such as organic or inorganic base materials and have excellent adhesive functions, so they have been used in many industrial fields, such as riser heat insulation materials, building materials, molding materials, etc. It is widely used as an industrial resin binder for grindstones and other products, depending on the purpose of use, but mostly in powder form.

Problems to be Solved by the Invention The powdered phenolic resin is usually sieved through a JIS standard sieve 20.
Because it is a fine powder that contains at least 80% by weight of what passes through a 0 mesh (74μ), it is scattered as dust during the packaging process at the production site, or at various processes such as measuring, compounding, and mixing at the site of use, and pollutes the work environment. or may adhere to workers' bodies, causing problems such as contact dermatitis. Therefore, from the standpoint of occupational safety and health, it is necessary to install local dust collection equipment and wear protective equipment. Measures are being taken.

However, such measures have problems such as economic burdens such as equipment costs and operating costs, economic losses due to scattering, and decreased work efficiency due to loss of work comfort. There is a strong desire to develop a powdered phenolic resin that has excellent dust resistance without impairing its performance as a binder.

The present invention has been made to solve the problems of the prior art described above, and its purpose is to provide a powdered phenolic resin composition with excellent dustproof properties and a method for producing the same, thereby making it easier to use at production or use sites. The purpose is to prevent the deterioration of the environment and workers from suffering from the disease (contact dermatitis), and at the same time, to reduce the economic burden such as the above-mentioned equipment costs and operating costs, as well as the economic loss caused by scattering.

Means for Solving the Problems In order to meet the demands of related industries that use the above-mentioned powdered phenolic resin, the present inventors have conducted extensive research with the aim of developing a powdered phenolic resin with excellent dustproof properties. As a result, by mixing and dispersing a specific amount of a specific ester compound and/or oil into the powdered phenolic resin of the prior art,
The present invention has been achieved by successfully developing a powdered phenolic resin composition that can prevent dust generation without impairing its performance as a binder.

That is, according to the present invention, powdered phenolic resin 100
At least one ester compound selected from the group consisting of phosphoric acid esters, aliphatic carboxylic acid esters, and aromatic carboxylic acid esters and/or oils having a boiling point of 200° C. or higher in liquid form based on the weight part A powdered phenol resin composition with excellent dustproof properties is provided, which contains .5 to 3 parts by weight of the powder.

Such a powdery phenol resin composition having excellent dustproof properties is prepared by adding at least one phenolic compound selected from the group consisting of phosphoric acid esters, aliphatic carboxylic acid esters, and aromatic carboxylic acid esters, and A mixture consisting of oils, these ester compounds, and powdery substances that are substantially incompatible with the oils is prepared, and then 0.3 to 3 parts by weight of the above-mentioned oil is added to 100 parts by weight of the phenolic resin. It is produced by blending the mixture containing the ester compound and/or oil and co-pulverizing it.

Examples of the powdered phenolic resin used in the present invention include phenol, resorcinol, catechol xylenol,
At least one phenolic compound such as alkylphenols whose alkyl group has 01 to C5 carbon atoms, bisphenols such as bisphenol A and bisphenol F, and at least one aldehyde such as formalin, paraformaldehyde, hexamine, or a substance with the same effect as these. Novolac-type phenolic resins, resol-type phenolic resins, benzylic ether-type phenolic resins, mixed resins thereof, and modified phenolic resins modified as appropriate depending on the purpose of use,
For example, thermoplastic resins such as vinyl acetate resin, polyamide resin, polyacetal resin, fluororesin, acrylic resin, polyethylene resin, polypropylene resin, vinyl chloride resin, polystyrene resin, silicone resin, or epoxy resin, urea resin, melamine resin, etc. Examples include polymer blends with thermosetting resins, or modified phenolic resins modified with rubber, lignin, urea, melamine, aniline, etc.

Examples of the liquid ester compound having a boiling point of 200°C or higher used in the present invention include phosphoric acid esters, aliphatic carboxylic acid esters, aromatic carboxylic acid esters, and arbitrary mixtures thereof. Specific examples of such ester compounds include phosphate esters such as tributyl phosphate, tricresyl phosphate, triethyl phosphate, trisisopropylphenyl phosphate, trioctyl phosphate, and octyldiphenyl phosphate, butyl stearate, and stearin. Aliphatic carboxylic acid esters such as amyl acid, dioctyl adipate, dioctyl sebacate, diptyl sebacate and diptyl maleate, as well as dimethyl phthalate, diethyl phthalate, diptyl phthalate, diheptyl phthalate, dioctyl phthalate and phthalic acid. Examples include aromatic carboxylic acid esters such as diisodecyl.

On the other hand, the oils used in the present invention are liquid and have a boiling point of 200°C.
Any oil having the above properties can be used, such as various lubricating oils,
Examples include silicone oils, animal and vegetable oils, and the like. These oils can be used alone or in any mixture, and can also be used in combination with the above-mentioned ester compounds.

The amount of the ester compound and/or oil used is 0.3 parts by weight per 100 parts by weight of the liquid phenol resin.
A suitable range is 3 parts by weight, preferably 0.5 to 2 parts by weight. If the amount used is less than 0.3 parts by weight per 100 parts by weight of phenolic resin, no effect can be expected to prevent dust scattering, and on the other hand, if it exceeds 3 parts by weight, the performance as a binder will deteriorate. So I don't like it.

Such a powdered phenolic resin composition of the present invention can be obtained by preparing a mixture of the ester compound and/or oil and a powdery substance that is substantially incompatible with these, and then It is obtained by adding the above mixture in an amount containing 0.3 to 3 parts by weight of the ester compound and/or oil to 100 parts by weight of the phenol resin, and then co-pulverizing the mixture by a conventional method.

Such powdery substances include the ester compounds and/or
Or, it is necessary that it is substantially incompatible with oils and does not inhibit the adhesiveness of the phenol resin.

Such powdery substances include, for example, hexamethylenetetramine, calcium carbonate, particulate silicic acid, thermoplastic resin powder, etc., and these may be used alone or in a mixture of two or more.

Although there is no particular limitation on the amount of these powdery substances used, it is preferably used in a ratio of 1 to 70 parts by weight of the ester compound and/or oil per 100 parts by weight of the granular substances.

In addition to the above-mentioned components, the powdered phenolic resin composition according to the present invention may contain any conventionally commonly used additives, such as coupling agents, curing accelerators, mold release agents, surfactants, Fatty acid amides, coloring agents, and the like can be blended within a range that does not impair the purpose of the present invention.

EXAMPLES Next, the present invention will be explained in detail with reference to Examples and Comparative Examples, but it goes without saying that the technical scope of the present invention is not absolutely limited by these examples. Furthermore, "part j" and "%" are all based on weight unless otherwise specified.

Examples 1 to 5 and Comparative Examples 1 to 3 100 parts of hexamine and 3 parts of tricresyl phosphate were mixed in a small mixer, and then 1000 parts of flaky novolak resin was added and further mixed. A mixture was obtained. Next, this mixture is pulverized using a small atomizer to obtain the powdered phenolic resin composition of the present invention (
A) was obtained (Example 1).

The amount of tricresyl phosphate is 5 parts, 10 parts, respectively.
Powdered phenolic resin compositions (B) to (E) of the present invention were obtained according to the procedure of Example 1 except that the amounts were 20 parts and 30 parts (Examples 2 to 5). Also, for comparison, each
Powdered phenolic resin compositions (F) to (H) were obtained according to the procedure of Example 1, except that no tricresyl phosphate was added and the amount of tricresyl phosphate was 2 parts and 40 parts (Comparative Examples 1 to 3) ).

Powdered phenolic resin compositions (A) to (E) according to the present invention
) was comfortable to work with as there was no scattering of the powdered resin during the crushing process, but the resin compositions (F) and (G) of comparative examples
The powdered resin was scattered and contaminated the work area, making the work uncomfortable. Further, in the resin composition (H) containing a large amount of tricresyl phosphate, although no scattering of powdered resin was observed, the grinder was heavily contaminated due to adhesion to the grinder, making workability extremely difficult.

Examples 6-9 Except that tricresyl phosphate was replaced with butyl stearate, dioctyl adipate, diethyl phthalate, and turbine oil (YS502 manufactured by Nippon Oil Co., Ltd.) at 1% each based on the flaky novolac resin. Powdered phenolic resin compositions (1) to (L) of the present invention were obtained according to the procedure of Example 1.

In all resin compositions, there was no scattering of powder during the grinding operation, and the operation was comfortable.

Example 10 and Comparative Example 4 After blending 50 parts of calcium carbonate and 5 parts of tributyl phosphate in a small mixer and thoroughly kneading, 1000 parts of coarse granular ammonia aresol resin was added and further mixed to obtain a mixture. Next, this mixture was pulverized using a small atomizer to obtain the powdered phenolic resin composition of the present invention (M
) was obtained (Example 10).

For comparison, a powdered phenolic resin composition (N) was obtained according to the procedure of Example 10 except that tributyl phosphate was not used (Comparative Example 4).

With the resin composition (M), there was no scattering of powder during the grinding operation, making the work comfortable, but with the resin composition (N), the powder was scattering, contaminating the workplace, and the work was not comfortable. .

Test Example For the powdered phenolic resin compositions obtained in Examples 1 to 10 and Comparative Examples 1 to 4 above, test molded bodies were made according to the following procedure for making feeder heat insulators to evaluate block resistance and performance. The bending strength was measured. In addition, the state of scattering of the resin composition during operation was also observed.

In a small Henschel mixer, add 4000 parts of water and 6 parts of newspaper.
After mixing and defibrating for 5 minutes, the defibrated material was transferred to a mixing tank equipped with an agitator, and then pulp 3
3 parts of rock wool, 67 parts of rock wool, and 850 parts of No. 8 silica sand were added and mixed for 8 minutes, and further 50 parts of the powdered phenol resin composition described above was added and thoroughly mixed and dispersed to obtain a resin-containing slurry. Next, this slurry was put into a drainer and subjected to suction and hydrophilization to produce a wet mat-like molded body (225x225x3f)n) with a water content of 45%. The obtained molded body was baked in a hot air circulation dryer at a temperature of 200° C. for 3 hours, and then cooled to room temperature to obtain a hardened cloak-shaped molded body.

The results were as shown in Table 1. The test method is as follows.

Test method 1, normal bending strength is medium 1 from the hardened cloak-shaped molded product.
Rectangular specimen of 5mm x length 225m x thickness 301mm (
n = 10) were prepared and the bending strength was measured, and the average value was taken as the normal bending strength (kg/cIa).

2. The state of dust generation of the powdered phenol resin composition was visually observed by observing the state of scattering when the composition was introduced from a height of 20 cm above the water surface of the mixing tank.

3. The block resistance of the powdered phenol resin composition was determined by visually observing the block state after standing for 48 hours at a temperature of 40° C. and a relative temperature of 70%.

Effects of the Invention As is clear from the above explanation, the powdery phenolic resin composition according to the present invention, which is prevented from scattering dust, is free from dust induced by conventional powdery phenolic resin in the above-mentioned processes at the production or use site. Since there is no scattering of dust, it has favorable effects in terms of occupational safety and health, such as being able to prevent deterioration of the working environment and the occurrence of contact dermatitis due to adhesion to workers. Furthermore, this improvement in the working environment not only improves working efficiency, but also has the excellent effect of reducing the cost of pollution equipment and preventing economic losses due to scattering.

Claims (1)

[Claims] 1. Based on 100 parts by weight of powdered phenolic resin, a liquid selected from the group consisting of phosphoric acid esters, aliphatic carboxylic acid esters, and aromatic carboxylic acid esters having a boiling point of 200°C or higher. A powdery phenol resin composition having excellent dustproof properties, which contains at least one ester compound and/or 0.3 to 3 parts by weight of oil. 2. Powder that is substantially incompatible with at least one ester compound and/or oil selected in advance from the group consisting of phosphoric acid esters, aliphatic carboxylic acid esters, and aromatic carboxylic acid esters. The method is characterized by preparing a mixture consisting of such substances, and then blending the mixture containing 0.3 to 3 parts by weight of the ester compound and/or oil to 100 parts by weight of the phenol resin, and co-pulverizing the mixture. A method for producing a powdered phenolic resin composition having excellent dustproof properties.