JPS63117059A - Dust-proof phenolic resin composition - Google Patents

Abstract

PURPOSE:To improve powder fluidity, to keep a good working atmosphere, to improve working efficiency and to stabilize quality, by blending a phenolic resin with a wetting agent and calcium carbonate having a treated surface. CONSTITUTION:A resin compsn. contains a phenolic resin,a wetting agent and calcium carbonate having a treated surface. It is preferred that the wetting agent for use in preventing the phenolic resin from being scattered as dust is poorly compatible with the resin and lowly volatile. Preferred examples thereof are compds. which are liquid at an ambient temp. of about 35 deg.C and have a b.p. of not lower than 200 deg.C, such as phosphoric esters, organic carboxylic acid esters, oils and mixtures thereof. The phenolic resin is used in the form of a powder in the presence or absence of hexamine (curing agent). Calcium carbonate having a treated surface, which is used for improving powder fluidity can be obtd. by treating the surface of fine calcium carbonate powder with a resin acid, a fatty acid, a surfactant, lignin, etc.

Description

DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to a dust-proof powdered phenolic resin composition having improved powder flowability useful as a binder for organic or inorganic fillers. be.

[Conventional technology and problems]

Traditionally, thermosetting phenolic resins have been available in powder, particulate, and
It is easily miscible with organic or inorganic fillers such as fibers in a wide range of proportions, has excellent adhesive function, and has relatively good thermal properties, mechanical properties, electrical properties, etc.
In addition, because the material cost is low compared to other thermosetting resins, it is used in many industrial materials such as building components, forming materials, resin felt materials, refractories, riser heat insulation materials, and grindstone materials. , friction materials, insulation materials, ceramics, laminates,
It is useful in a variety of fields as an industrial resin binder for shell molds and other applications.

Generally, this type of phenolic resin is used in liquid, powder, or other forms depending on the purpose of use, and among these, it is particularly common to use it in powder form.

[Problem that the invention seeks to solve]

However, such powdered phenolic resins generally have a particle size of 74
Since it is a fine powder of less than μm in size, it is carried out when transferred to a storage tank or potper installed at the site of use, when spraying from an automatic resin sprayer, when automatically weighing, or as necessary. When handling such as blending or mixing, phenolic resin easily scatters as dust, worsening the working environment, significantly reducing work efficiency, and causing environmental health problems such as adhesion to the human body and causing health problems. In addition, problems such as variations in quality or increased manufacturing costs due to the dissipation of the phenol resin have become a problem.

In order to solve these problems, the present inventors conducted research and development on a powdered phenolic resin with excellent dustproof properties, and as a result, they previously published a suitable resin composition in Japanese Patent Application No. 60-223782. and proposed its manufacturing method.

However, under high temperature and high humidity conditions, the powder fluidity of the resin decreases, making it difficult to discharge the resin from storage tanks, hoppers, etc., or causing the resin to gradually accumulate in the transfer pipe and clog the pipe. Alternatively, when using automatic spraying machines or automatic weighing machines for phenolic resin, various problems may occur such as variations in the amount of resin sprayed or weighed, which may reduce work efficiency or interfere with ensuring stable quality. Problems such as the above are frequently experienced, and there is a strong desire from related industries to improve powder flowability.

The present invention was made to solve the problems of the prior art, and its purpose is to improve powder fluidity, thereby maintaining a comfortable working environment and improving work efficiency.
Another object of the present invention is to provide a dust-proof powdered phenolic resin composition that can stably ensure quality.

[Means for solving problems]

As a result of extensive research aimed at improving the powder fluidity of dust-proof powdered phenolic resin compositions, the present inventors discovered that surface-treated calcium carbonate has an outstanding effect as a powder fluidity imparting agent. Based on this knowledge, we have developed a dust-proof powdery phenolic resin composition that can solve the problems of the prior art, and have completed the present invention.

That is, the present invention provides a dust-proof phenolic resin composition with excellent powder fluidity, which contains a phenolic resin, a wetting agent, and surface-treated calcium carbonate as essential components.

The present invention will be explained in detail below.

The phenolic resin in the present invention is not particularly limited,
It is a solid phenolic resin obtained by heating and reacting at least phenols and aldehydes in the presence of a catalyst, such as novolac type phenol resin, resol type phenol resin,
Examples include enol resins, nitrogen-containing resol type phenolic resins, benzyl ether type phenolic resins, modified phenolic resins thereof, or any mixed resins thereof. Used as a powder form of existence.

The phenols include phenol, cresol,
Monohydric phenols such as xylenol, phenylphenol, para-tert-butylphenol, or alkyl-substituted phenols, or polyhydric phenols such as resorcinol, catechol, hydroquinone, pyrogallol, bisphenol A, bisphenol F, diphenolic acid, or For example, phenolic residues such as resorcinol residues, catechol residues, cresol residues, and xylenol residues, which are by-produced during the production of phenols, are exemplified, and these may be used alone or as a mixture of two or more. As the aldehyde, for example, formalin, paraformaldehyde, trioxane, hexamine, or a mixture thereof at various concentrations can be used. It is also possible to use glyoxal, furfural, etc. in combination, if necessary.

The amount of aldehydes to be blended with respect to phenols is selected depending on the resin type and desired performance, and is generally not limited, but usually in the case of novolak type phenolic resins, the amount of aldehydes per mole of phenols is 0. 5-0
．． In the case of a resol type phenolic resin or a benzyl ether type phenolic resin, the amount of aldehyde is appropriately selected within the range of 1.0 to 5.0 mol per 1 mol of phenol.

In addition, as a catalyst, conventionally commonly used acidic catalysts or basic catalysts, such as inorganic or organic acids such as hydrochloric acid, sulfuric acid, oxalic acid, para-toluenesulfonic acid, Mn, Zn,
Carboxylic acid metal salts such as Pb and naphthenic acid metal salts or boric acid metal salts, Lewis acids such as zinc chloride, sodium hydroxide,
Alkali metal hydroxides such as potassium hydroxide, alkaline earth metal oxides or hydroxides such as magnesium oxide and calcium hydroxide, carbonates such as potassium carbonate and sodium hydrogen carbonate, and basic compounds such as trisodium phosphate. phosphorus compounds,
These include amine compounds such as ammonia, hexamine, and quaternary ammonium hydroxide salts.

These catalysts may be used alone or in combination of two or more of the same type, or an acidic catalyst or a basic catalyst may be used in combination at intervals.

Furthermore, as a modifier used when preparing a modified phenolic resin by reacting or mixing it during the production of the phenolic resin or mixing it after the production as desired,
For example, nitrogen-containing compounds such as urea, melamine, aniline, and guanamine, salicylic acid, furfuryl alcohol, cashew nut shell oil, tall oil, lignin, epoxy resin, xylene acid fat, urea resin, melamine resin, vinyl acetate resin, and polyamide resin. , acrylic resin, etc.

The wetting agent used to prevent dust generation from the phenolic resin is preferably one with low volatility and low compatibility with the resin.
For example, it is liquid at an environmental temperature of about 35°C, and
Preferred are phosphoric acid esters, organic carboxylic acid esters, oils, or mixtures thereof having a boiling point of 00°C or higher.

Typical specific examples of these wetting agents include tributyl phosphate, tricresyl phosphate, triethyl phosphate,
Phosphate esters such as trisisopropylphenyl phosphate, trioctyl phosphate, octyldiphenyl phosphate,
Butyl stearate, amyl stearate, dioctyl adipate, dioctyl sebacate, dibutyl sebacate, dibutyl maleate, dimethyl phthalate, diethyl phthalate, dibutyl phthalate, dihebutyl phthalate, dioctyl phthalate, diisodecyl phthalate, phthalic acid Organic carboxylic acid esters such as diallyl and butyrolactone, liquid paraffin, heavy oil, lubricating oil, spindle oil,
Hydrocarbon oils such as turbine oil and machine oil, silicone oils such as polydimethylsiloxane and polyphenylmethylsiloxane, fluorine oils such as trifluorochloroethylene low polymers, linseed oil, olive oil, tung oil, rapeseed oil, Examples include animal and vegetable oils such as soybean oil, cottonseed oil, camellia oil, coconut oil, castor oil, sesame oil, whale oil, and herring oil.

The blending amount of this wetting agent varies depending on the type and particle size of the phenolic resin, the type of wetting agent, the presence or absence of other additives, etc. - Although not generally limited, it is usually 5 parts by weight per 100 parts by weight of the phenolic resin. It is suitably less than 0.01 to 3 parts by weight, preferably 0.01 to 3 parts by weight. If this amount exceeds 5 parts by weight, a large amount of surface-treated calcium carbonate is required to obtain practical powder flowability, which is not only uneconomical but also reduces the performance as a binder, which is preferable. do not have.

The surface-treated calcium carbonate used in the present invention to improve powder fluidity may be treated with a resin acid or resin acid-based surface treatment agent, a fatty acid or fatty acid-based surface treatment agent, or a surfactant (e.g., a cationic surface treatment agent). , sulfonic acid type, sulfuric acid ester type, fatty acid type, etc.), lignin, polyacrylic acid type surface treatment agent, paraffin type surface treatment agent, silicon compound, or other surface treatment agent, and this is treated with natural rubber, Synthetic rubber, various synthetic resins,
This name is used in the industry as a reinforcing filler that is added to paints, inks, paper, etc. to improve their physical properties (e.g. mechanical properties, electrical properties, thermal properties, etc.) and improve processability. It is widely known for its products, and many products are actually known for it. For example, as calcium carbonate surface treated with resin acid, Shiroenka 0, Shiroenka DD, Shiroenhana AA, Shiroenhana TDD, Homocal D, Homocal DM, U
nifant-15 (product name manufactured by Shiraishi Kogyo Co., Ltd.),
MC-7, MT-100, HSK-(: (Top, product name manufactured by Maruo Calcium Co., Ltd.) As calcium carbonate surface-treated with fatty acid or fatty acid-based surface treatment agent, Hakuenhana CC1 Hakuenhana CCR1 Hakuenhana RO6, Gelton 50, ViHot-
15, StaVigot-15^ (all of the above are product names manufactured by Shiraishi Kogyo Co., Ltd.) MSK-B, Calfein 200, MSK-^
, HSK-PO, Calfein 100, MC-T, M
C-5 [, Snow Light SSS, Snow Light SS, M
White, MC Coat 5-1 (trade name manufactured by Maruo Calcium Co., Ltd.), Rydon B5-0, Rydon A (trade name manufactured by Bihoku Funka Kogyo Co., Ltd.), calcium carbonate surface treated with cationic surfactant. Shiroenka U (trade name, manufactured by Shiraishi Kogyo Co., Ltd.) as calcium carbonate, Calmos (trade name, manufactured by Shiraishi Kogyo Co., Ltd.) as calcium carbonate surface-treated with lignin, MP-777 as calcium carbonate surface-treated with a polyacrylic acid surface treatment agent, MP-1000, MP-Z (all trade names manufactured by Maruo Calcium Co., Ltd.), MSK- as calcium carbonate surface-treated with a silicon-based compound, FP-1 (
The above is a product name manufactured by Maruo Calcium Co., Ltd.), 5L-101,5
L-151, TS Powder H50 (trade name manufactured by Shiraishi Kogyo Co., Ltd.), MC Coat P-1 (trade name manufactured by Maruo Calcium Co., Ltd.) as calcium carbonate surface-treated with paraffin.
It is commercially available as etc. Among these, those having an average particle size of 1 μm or less are preferable, and it can be said that generally, the smaller the particle size, the greater the effect of improving powder fluidity.

The average particle diameter of the surface-treated calcium carbonate used in the present invention is determined from the specific surface area measured with a constant pressure aeration type specific surface area measuring device using the following formula.

8. The amount of surface-treated calcium carbonate used in the present invention depends on the type and particle size of the phenolic resin, the type and amount of the wetting agent, the type and particle size of the calcium carbonate, the presence or absence of other additives, and the desired powder. The amount varies depending on fluidity and the like, but is generally not limited to 15 parts by weight or less, preferably 0.1 to 10 parts by weight, per 100 parts by weight of the phenolic resin. If the blending amount exceeds 15 parts by weight, the effect of improving powder fluidity is small and not only is it uneconomical, but it is also undesirable because it causes a decrease in performance as a binder.

In addition, the surface-treated calcium carbonate used as a powder fluidity imparting agent in the present invention is the powder fluidity imparting agent commonly used in the past, such as higher fatty acid salts such as calcium stearate, methylene bisstearamide, etc. It is also possible to use it in combination with higher fatty acid amides, polyethylene, waxes such as wax, fine particle silicic acid compounds such as ^EROSrL, white carbon, talcum powder, mica powder, etc.

The method for producing the dust-proof phenolic resin composition with excellent powder flowability of the present invention is not particularly limited, but for example, first, a wetting agent and a powdered carrier that is substantially incompatible with the wetting agent are mixed. A wetting agent-carrier mixture is prepared by mixing thoroughly, and then the above mixture and surface-treated calcium carbonate or additives such as a mold release agent are added as necessary to the solid phenolic resin (base resin). A method of pulverizing and mixing using a conventional pulverizer is preferable.

The powder-like carrier is preferably one with as fine a particle size as possible, such as hexamine powder, thermoplastic resin powder, calcium carbonate powder, fine-grained silicon compound, etc. In particular, hexamine powder used as a hardening agent for resins, or thermoplastic Resin powder etc. are suitable. The amount of the carrier other than hexamine is appropriately selected within a range that does not impair the function of the binder, but it is usually phenolic resin 100%
A suitable amount is 10 parts by weight or less.

In addition to the above-mentioned components, the phenolic resin composition of the present invention may optionally contain any additives commonly used in the past, such as silane coupling agents such as amine silanes and epoxy silanes. or resin acid amides such as ethylene bisstearamide, oxystearamide, stearamide, methylolamide, waxes such as polyethylene wax, paraffin wax, carnauba wax, calcium stearate, zinc stearate, magnesium stearate, etc. mold release agents such as stearates, or aromatic carboxylic acids such as benzoic acid, salicylic acid, and aminocarboxylic acids;
Polyhydric phenols such as resorcinol, catechol, bisphenol A and bisphenol S, alkaline earth metal hydroxides or oxides such as calcium hydroxide, barium hydroxide, and magnesium oxide, aromatic amines such as aniline, diaminodiphenylmethane, and phenylenediamine, etc. A curing accelerator may be added within a range that does not impair the object of the present invention.

〔Example〕

The present invention will be specifically explained using examples, applied examples, and comparative examples, but the technical scope of the present invention is not limited by these examples. All "parts" and "1%" are by weight unless otherwise specified.

1 to 8 and 1 After weighing out 3 parts of wetting oil (trade name: M Oil, product of Nippon Oil Co., Ltd.) as a wetting agent and 100 parts of hexamine, which also serves as a carrier for the wetting oil and a curing agent for the novolac resin, mix them in a mixer. A wetting agent/hexamine mixture was prepared by mixing thoroughly.

Next, a mixture was prepared consisting of 1,000 parts of flaky novolac resin, the entire amount of the wetting agent/hexamine mixture, and 30 parts of surface-treated calcium carbonate (trade name: Hakuenka 0, product of Shiraishi Kogyo Co., Ltd.) as a powder fluidity imparting agent, and the mixture was prepared using an atomizer. - to obtain a powdered phenol resin composition (A). (Example 1) Hereinafter, based on the composition shown in Table 1, seven types of powdered phenol resin compositions were prepared in the same manner as in Example 1 except that another surface-treated calcium carbonate was used in place of efflorescence. Products (B) to (H) were obtained and designated as Examples 2 to 8.

In addition, for comparison with the above example, untreated calcium carbonate (trade name: Br1) was used instead of surface-treated calcium carbonate.
A powdered phenolic resin composition (I) was obtained as Comparative Example 1 by carrying out the same operation as in Example 1 except that lliant-1500, a product of Shiraishi Kogyo Co., Ltd.) was used. Examples 9 to 11 The same procedure as in Example 1 was carried out except that the amounts of lubricating oil and white luster 0 were changed based on the composition shown in Table 1.
Different types of powdered phenolic resin compositions (J+) to (J3) were obtained, which were designated as Examples 9 to 11.

K1 Takumi 11 After weighing out 15 parts of silicone oil as a wetting agent and 50 parts of polyvinyl chloride resin powder (hereinafter abbreviated as PVC powder) as a carrier for the wetting agent, they were thoroughly mixed in a mixer to form silicone oil-PVC. A powder mixture was prepared. Next, 1000 parts of coarse granular ammonia aresol resin, the above silicone oil-pv
A mixture consisting of the total amount of the powder mixture and 050 parts of White Glossy Flower as a powder fluidity imparting agent was prepared, and the mixture was pulverized and mixed with an atomizer to obtain a powdered phenol resin composition (I).

Nine types of powdered phenolic resins were prepared in the same manner as in Example 1, except that the type and amount of lubricant and the amount of Hakuenka○ were changed based on the composition shown in Table 1. Composition(
L+) to (N) were obtained, and these were designated as Examples 13 to 21.

Hii "Lλgo" - Powdered phenolic resin composition (0) without using a powder fluidity imparting agent and powdered phenolic resin composition without using a wetting agent or powder fluidity imparting agent for comparison with the above example. Comparative Example 2 and Comparative Example 3 were prepared using the same procedure as in Example 1 based on the composition shown in Table 1.

Regarding the powdered phenolic resin compositions obtained in the above Examples or Comparative Examples, the powder fluidity and dust generation properties of each were investigated using the following test methods.

The results are shown in Table 1.

Measurement of r -1 and detection of dust The limit diameter of the outflow at which a certain amount of powdered phenolic resin filled in a rectangular parallelepiped container with sides of 60 mm can freely fall from the outlet provided at the bottom of the container is set to 5 mm square. Powder fluidity was evaluated by determining the interval.

In addition, the dust generation status of the powdered phenol resin, which is observed in the measurement of powder fluidity, was visually determined.

The evaluation display is as follows.

◎...No dust generation ○...Some dust generation ×...
Severe dust generation.

As shown in Table 1 below, the resin composition of the present invention using surface-treated calcium carbonate has better powder flowability than the resin composition using untreated calcium carbonate (Comparative Example 1). It was confirmed that surface-treated calcium carbonate is very effective as a fluidity improver for powdered resin.

Further, as shown in Example 1, it was found that even if surface-treated calcium carbonate was blended in such a large amount that the performance as a binder was degraded, the efficiency of improving powder fluidity was small and uneconomical.

Further, the identification of calcium carbonate contained in the powdered phenolic resin composition can be carried out by the following analysis method, which is very useful for quality control such as prevention of work errors.

That is, a powdered phenolic resin composition (containing calcium carbonate) is added to a 30% NaBr aqueous solution containing a small amount of surfactant (for example, Libon F), thoroughly shaken and dispersed, and then centrifuged to separate the resin layer (the second layer). 1 layer), an aqueous NaBr solution (2nd layer) and a precipitate (3rd layer). Then, after removing the first and second layers, the NaB
After adding an aqueous solution and repeating the same operation, a precipitate is obtained by washing with water, separating (centrifuge), filtering, and drying.

The presence or absence of surface treatment can be determined by measuring the precipitate obtained by the above pretreatment using an infrared absorption spectrum (IR) and determining the difference spectrum from that of untreated calcium carbonate. Furthermore, after extracting organic substances from the precipitate with an organic solvent such as methanol, the amount of the surface treatment agent can be determined by determining the amount of the surface treatment agent and determining the loss on ignition (900°C x 60 minutes) using an IR method, GPC method, etc. It is possible to understand.

Kuzushin 1 Put 4000 parts of water and 67 parts of newspaper into a Henschel mixer, mix and defibrate for 5 minutes, then transfer this to a mixing tank, and add 33 parts of valve, 67 parts of rock wool, and 850 parts of No. 8 silica sand. was added and mixed for 8 minutes.

Furthermore, 50 parts of the powdered phenolic resin composition (G) obtained in Example 7 was added and thoroughly mixed and dispersed to obtain a resin-containing slurry. Next, this slurry was put into a drainer and dehydrated by suction to produce a mat-like molded body with a water content of 45%, which was heated in a hot air heating furnace at a temperature of 200°C for 3 hours.
After firing for a period of time, the molded product was cooled to room temperature to obtain a cured molded product that can be used as a heat insulating material for a riser.

A test piece for bending strength measurement (
A length of 225s+n+ x width of 15mm x thickness of 301) was produced.

In addition, as a comparison control, the powdered phenolic resin composition (P) obtained in Comparative Example 3 was used instead of the above resin composition (G).
Test pieces were prepared in the same manner as above, except that the test pieces were used, and the bending strength of each was measured using a universal testing machine.

In addition, the dust generation observed when the resin composition was introduced into the mixing tank was visually determined. The results are shown in Table 2, and it was confirmed that the resin composition of the present invention did not generate dust and exhibited strength comparable to conventional resin compositions, and had sufficient practicality as a binder. .

2nd side and Takumi 2 After blow-filling the resin coated sand prepared by the dry hot coating method into a mold whose temperature is controlled to 250℃,
A dog bone mold was produced by firing for 1 minute.Then, this mold was cut from the center (6.5 am2 in cross-sectional area), preheated in a thermostat (ambient temperature 200°C) for 15 minutes, and the mold pieces were cut into pieces. Take it out and immediately apply Example 2 to one cut surface.
The powdered phenolic resin composition (M) obtained in 0.0
The other mold piece was crimped and cooled to room temperature to prepare a test piece for measuring adhesive strength.

Also, for comparison, instead of the above resin composition (M),
Conventional powdered phenolic resin composition prepared in Comparative Example 3 (
Test pieces were prepared in the same manner as above except for using P), and the adhesive strength of each was measured using a tensile strength tester. The results are shown in Table 4, and it was confirmed that the resin composition of the present invention exhibited superior strength to conventional resin compositions, and could be sufficiently used as a binder for practical use.

Table 3 [Effects of the Invention] As is clear from the above description, the dust-proof powdered phenolic resin composition of the present invention having improved powder fluidity has the following effects, and can be used in various applications. It has extremely high industrial utility.

(1) This measure was implemented as a countermeasure to dust problems generated from equipment such as storage tanks, hoppers, transfer pipes, automatic spreaders, automatic weighers, etc. at manufacturing sites, or resin discharge or blockage problems that tend to occur in hot and humid conditions. Since the noise problem caused by the use of vibrators, etc. attached to the above-mentioned equipment can be resolved, the working environment will not only be greatly improved, but it will also be more comfortable, contributing to the prevention of health problems caused by adhesion to the human body, etc. It is possible to provide a comfortable working environment and improve work efficiency.

(2) Spreading and weighing of phenolic resin can be carried out smoothly using automatic spraying machines and automatic weighing machines, which prevents variations in quality and decreases in work efficiency that previously occurred due to this type of trouble. , it is possible to improve production efficiency while ensuring stable quality.

(3) Since dissipation of the resin is prevented, the rate of resin fixation to various fillers, etc. is improved, and it is possible to improve quality or reduce manufacturing costs.

Moreover, the dustproof powdery phenolic resin composition of the present invention is
Fireproofing of resin felt materials, feeder heat insulation materials, building materials such as mineral boards and fiberboards, inorganic fiber insulation materials, grindstone materials, friction materials, ceramics, carbon materials, graphite materials, unfired brick materials, blast furnace closing materials, etc. It is suitably used as an industrial resin binder for various applications such as objects, shell molds, mold or core adhesives, molding materials, and industrial laminate materials.

Claims (1)

[Claims] 1. A dust-proof phenolic resin composition with excellent powder fluidity, which contains a phenolic resin, a wetting agent, and surface-treated calcium carbonate as essential components. 2. Claim 1, wherein the wetting agent is at least one liquid compound selected from the group of phosphoric acid esters, organic carboxylic acid esters, and oils with a boiling point of 200°C or higher.
The resin composition described in .