JP2014084445A - Method of producing powder resin mixture having low dust producing properties, powder having low dust producing properties, method of reducing dust production of resin, and method of producing molded article - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a powder resin mixture having low dust producing properties, which is suppressed in dust producing properties during use.SOLUTION: The method of producing the powder resin mixture having the low dust producing properties comprises the steps of: preparing a powder having the low dust producing properties, which includes a thermosetting resin and liquid paraffin; and obtaining the powder resin mixture having the low dust producing properties by dry-mixing the powder having the low dust producing properties and a filler.

Description

  The present invention relates to a method for producing a low dusting powder resin mixture, a low dusting powder, a resin dusting method, and a molded product production method.

  There are the following methods for reducing dust generation of fine powder or powder.

  Patent Document 1 describes a method for reducing dust generation of fine powder that easily scatters as dust during operations of slaked lime, dolomite, calcium carbonate, cement, gypsum, slag, magnesium hydroxide, and the like. Specifically, attempts have been made to reduce the dust generation of the fine powder by mixing the branched polyethyleneimine solution with the fine powder.

  Patent Document 2 describes a method for reducing dust generation, such as slaked lime, light calcined dolomite, cement, gypsum, slag, coke powder, and diatomaceous earth, whose properties change when water is added. ing. Specifically, attempts have been made to reduce powder dust generation by mixing a branched polyethyleneimine solution using an organic solvent as a solvent with the powder.

  As described in Patent Document 1-2, there is a method for suppressing dust generation of a powdery low-molecular compound. However, for example, there has never been a method for suppressing dust generation of a powdery polymer compound such as a thermosetting resin.

  Among these polymer compounds, thermosetting resins are known to have high polarity in themselves and are difficult to mix with compounds generally used as lubricants.

Japanese Patent Laid-Open No. 10-226780 Japanese Patent Laid-Open No. 11-80712 JP 2011-214002 A

  The thermosetting resin is used in a powder state when normally used. Since it is powdery at this time, there is a problem that the thermosetting resin generates dust and easily diffuses to the surroundings. If the thermosetting resin is dusted during use, the resin is sprayed into the work space, for example, the work space is contaminated, powder resin is mixed into the work device, mixed with other reagents, etc. Sometimes happened.

  In order to solve the above problems, the present inventor has found that dusting of the powdered resin composition can be suppressed by adding liquid paraffin to the thermosetting resin, and has reached the present invention.

  This invention is made | formed in view of the said situation, and provides the powder resin mixture by which the dust generation property at the time of use was suppressed.

According to the present invention, preparing a low dusting powder containing a thermosetting resin and liquid paraffin;
A step of dry-mixing the low dusting powder and the filler to obtain a low dusting powder resin mixture;
A process for producing a low dusting powder resin mixture is provided.

  Conventionally, liquid paraffin is added as a lubricant for improving fluidity and releasability of a resin when a thermoplastic resin is thermoformed.

  Here, the fluidity is an index indicating the behavior of the resin when pressure is applied during heating and melting. For this reason, it is generally known that a lubricant is not added to a thermosetting resin in which the fluidity of the resin is significantly reduced by heating.

  Here, the dust generation property of the thermosetting resin can be suppressed by mixing liquid paraffin with the thermosetting resin before molding. The reason is not necessarily clear, but is considered as follows. When liquid paraffin is added to the thermosetting resin, static electricity is generated. As a result, it is considered that electrostatic attraction acts between the fine particles, and the fine particles can be prevented from rising.

  The thermosetting resin is preferably a phenol resin or an epoxy resin, and the liquid paraffin preferably contains an alicyclic component. By doing so, the resin and liquid paraffin are easily mixed uniformly.

Furthermore, according to the present invention, the low dust generation powder used in the method for producing the low dust generation powder resin mixture,
A thermosetting resin;
Liquid paraffin,
A low dusting powder is provided.

  Furthermore, according to the present invention, there is provided a resin dust generation method that reduces the amount of dust generation by adding liquid paraffin to a molten thermosetting resin.

  Furthermore, according to this invention, the manufacturing method of a molded article including the process of obtaining a molded article from the low dust generation powder resin mixture obtained by the manufacturing method of the said low dust generation powder resin mixture is provided.

  ADVANTAGE OF THE INVENTION According to this invention, the powder resin mixture by which the dust generation property at the time of use was suppressed is provided.

  The method for producing a low dust generation powder resin mixture according to the present embodiment comprises a step of preparing a low dust generation powder containing a thermosetting resin and liquid paraffin, a dry mix of the low dust generation powder, and a filler. And obtaining a low dusting powder resin mixture.

(Low dusting powder)
The low dust generation powder according to the present embodiment includes a thermosetting resin and liquid paraffin in the low dust generation powder. By doing so, it is possible to provide a low dusting powder that is more excellent in suppressing dusting. The reason is not necessarily clear, but is considered as follows. When liquid paraffin is added to the thermosetting resin, static electricity is generated. As the static electricity is generated, the charge amount of the powder is improved. That is, an electrostatic attractive force due to electric charges acts between the fine particles forming the powder. This force is considered to suppress the rising of each fine particle generated when using the powder and to suppress the dust generation.

The average particle size _{d 50} of the low dusting powder according to the present embodiment further preferably preferably at 1μm or more 500μm or less, if it is 5μm or 100μm or less. When the average particle size of the low dusting powder is in this range, the degree of dusting suppression during use can be further improved.

  Moreover, although the produced low dust generation powder is not specifically limited, For example, it uses using the method demonstrated below.

First, dry mix the low dusting powder with various fillers. Here, the dry mix indicates that the low dusting powder and the filler are mixed without melting. Further, when dry mixing the low dusting powder with various fillers, each component may be heated, but a form such as heat kneading in which any of them is melted and kneaded is not used.
In this way, by using the low dusting powder according to the present embodiment, it is possible to prevent the powder from being diffused and generate dust, so that the work space that has conventionally occurred is contaminated. It is possible to prevent the powder resin from being mixed into the apparatus, mixing into other reagents, and the like.

  Here, the various fillers are not particularly limited. For example, abrasive grains, inorganic fillers, organic fillers, silica sand, curing agents, coupling agents, rubber, base materials, solvents, pigments, fibers, and surfactants. Agents, flocculants, hair materials, foaming agents, glass, aggregates, carbon, acids and the like.

  Thereafter, the low dusting powder resin mixture obtained by dry mixing is not particularly limited, but for example, heat kneading, melt molding, hot forming, hot working, applying to a substrate, etc. It is used by various methods such as fixing to a raw material for production and impregnating a base material. By carrying out like this, the molded article containing the low dust generation powder which concerns on this embodiment can be obtained.

  Further, the low dusting powder resin mixture is used in the above method as a resin material or a molding material for obtaining various manufactured products described below. The low dust-generating powder resin mixture includes, for example, (1) a resin material for obtaining a grindstone such as a general grinding wheel, a heavy grinding grindstone, a cutting grindstone, an offset grindstone, a glass cloth treatment, a diamond grindstone, and (2) a polishing cloth. Resin materials for obtaining abrasive cloth such as abrasive paper, disc sandpaper, abrasive bab, (3) Shell mold method (cold coat, semi-hot coat, dry hot coat), organic self-hardening (cold box, phenol urethane, (Phenolic acid curing, linocure, furan, organic acid ester), hot box, shell adhesive, resin material for obtaining castings such as mold material, (4) Brake lining, clutch facing, disc pad, paper clutch facing, control wheel Resin materials for obtaining friction materials such as (5) rubber reinforcement, hot melt adhesives, Adhesive tape, rubber adhesive compounding, rubber latex compounding, tackifier, pressure sensitive adhesive, metal adhesive compounding, rubber vulcanization, resin material for obtaining rubber such as sealing material, (6) Capacitor coating, insulating varnish (7) Paint bases, oil-modified paints, furniture paints, paints for metal cans, printing inks, offset printing, dyeing assistants, photoresists and other paints and printing inks (8) Resin material for obtaining organic materials such as felt, phenol foam, wood powder molding, phenol resin fiber, hard board, particle board, reinforced wood, insulation board, etc., (9) Beater Additives, resin materials for obtaining pulp-impregnated products such as battery separators, air filters, oil filters, (10) glass fibers Products (mats, heat insulation cylinders), rock wool / slag wool products, resin materials for obtaining inorganic fiber bonded products such as fishing rods, (11) irregular shaped materials (mud materials, spray materials, stamp materials, throwing materials, press-fitting materials , Castable), shaped material (basic non-fired, charcoal and silica fired, sliding nozzle, immersion nozzle), hot water insulation, tundish board, aggregate primary binder, crucible and other resin materials for obtaining refractory products , (12) Plywood (special), laminated wood, resin materials for obtaining woodworking adhesives such as panel adhesives, (13) impervious carbon products, carbonaceous sealing materials, electric brushes, sliding materials, activated carbon It is used as a resin material for obtaining other products such as corrosion-resistant joint agents, epoxy resin curing agents, casting, phenol FRP, and the like.

(Thermosetting resin)
The thermosetting resin contained in the low dust generation powder according to the present embodiment is not particularly limited. For example, phenol resin, epoxy resin, melamine resin, urea resin, oxetane resin, (meth) acrylate resin , Unsaturated polyester resin, diallyl phthalate resin, maleimide resin, or the like is used. Moreover, these can also be used individually or in combination of 2 or more types. Among these, it is preferable to use a phenol resin or an epoxy resin.

  When phenol resin or epoxy resin is used, mixing with liquid paraffin tends to be uniform. For this reason, the suppression of dust generation during use is more excellent.

The phenol resin in this embodiment is obtained by reacting phenols and aldehydes in the presence of an alkaline or acidic catalyst, and has at least one phenolic hydroxyl group in the aromatic ring. ing.
Examples thereof include a phenol resin, a cresol resin, a resorcin resin, a xylenol resin, a naphthol resin, a bisphenol A resin, an aralkyl phenol resin, a biphenyl aralkyl phenol resin, and a modified phenol resin using cashew nut oil having a phenolic hydroxyl group. Also used are xylene-modified phenol resins containing substances having phenolic hydroxyl groups, and various modified phenol resins such as phenol-modified rosin, oil-modified phenol resins modified with terpene oil, rubber-modified phenol resins modified with rubber, etc. can do.

  As the phenols used for obtaining the phenol resin, those having a phenolic hydroxyl group in the aromatic ring are preferable, and further, a substituent other than the phenolic hydroxyl group may be included. For example, cresols such as phenol, o-cresol, m-cresol, p-cresol, mixed cresol, 2,3-xylenol, 2,4-xylenol, 2,5-xylenol, 2,6-xylenol, 3,4- Xylenol, xylenol such as 3,5-xylenol, ethylphenol such as o-ethylphenol, m-ethylphenol and p-ethylphenol, butylphenol such as isopropylphenol, butylphenol and p-tert-butylphenol, p-tert-amylphenol Alkylphenols such as p-octylphenol, p-nonylphenol and p-cumylphenol, halogenated phenols such as fluorophenol, chlorophenol, bromophenol and iodophenol, p-phenol Monohydric phenol substituents such as ruphenol, aminophenol, nitrophenol, dinitrophenol, trinitrophenol, and monovalent naphthols such as 1-naphthol and 2-naphthol, resorcin, alkylresorcin, pyrogallol, catechol, alkylcatechol, Examples thereof include hydroquinone, alkylhydroquinone, phloroglucin, bisphenol A, bisphenol F, bisphenol E, bisphenol S, and cashew nut oil composed of a substance having a phenolic hydroxyl group, such as dihydroxynaphthalene. These can be used alone or in combination of two or more. Moreover, you may use the copolymer of the phenols which have these phenolic hydroxyl groups, and the substance which does not contain other phenolic hydroxyl groups. Thereby, the phenol resin which has at least 1 or more phenolic hydroxyl group in a molecule | numerator can be obtained.

  Examples of the aldehydes used to obtain the phenol resin include formaldehyde, paraformaldehyde, trioxane, acetaldehyde, propionaldehyde, polyoxymethylene, chloral, hexamethylenetetramine, furfural, glyoxal, n-butyraldehyde, capro Examples include aldehyde, allyl aldehyde, benzaldehyde, crotonaldehyde, acrolein, tetraoxymethylene, phenylacetaldehyde, o-tolualdehyde, salicylaldehyde, paraxylene dimethyl ether and the like. These may be used alone or in combination of two or more.

  It does not specifically limit as a method of making the said phenols and aldehydes react, A well-known method is employable.

  The catalyst for obtaining the phenol resin is not particularly limited, and examples thereof include an acid catalyst, a base catalyst, and a transition metal salt catalyst. Examples of the acid catalyst include inorganic acids such as hydrochloric acid, sulfuric acid, and phosphoric acids, and organic acids such as oxalic acid, p-toluenesulfonic acid, and organic phosphonic acid. Examples of the base catalyst include alkali metal hydroxides such as sodium hydroxide, potassium hydroxide and lithium hydroxide, alkaline earth metal hydroxides such as calcium hydroxide and barium hydroxide, ammonia, alkylamine and the like. These amines can be used. Furthermore, examples of the transition metal salt catalyst include zinc oxalate and zinc acetate.

  Examples of the epoxy resin include novolak type epoxy resins such as phenol novolac type epoxy resin and cresol novolak type epoxy resin; bisphenol type epoxy resins such as bisphenol A type epoxy resin and bisphenol F type epoxy resin; N, N-di Aromatic glycidylamine type epoxy resins such as glycidylaniline, N, N-diglycidyltoluidine, diaminodiphenylmethane type glycidylamine, aminophenol type glycidylamine; hydroquinone type epoxy resin; biphenyl type epoxy resin; stilbene type epoxy resin; Methane-type epoxy resin; Triphenolpropane-type epoxy resin; Alkyl-modified triphenolmethane-type epoxy resin; Triazine nucleus-containing epoxy resin; Dicyclopenta En-modified phenol type epoxy resin; naphthol type epoxy resin; naphthalene type epoxy resin; naphthylene ether type epoxy resin; phenol aralkyl type epoxy resin having phenylene and / or biphenylene skeleton, naphthol aralkyl type epoxy having phenylene and / or biphenylene skeleton Examples thereof include aralkyl-type epoxy resins such as resins, and aliphatic epoxy resins such as alicyclic epoxies such as vinylcyclohexene dioxide, dicyclopentadiene oxide, and alicyclic diepoxy-adipade. These may be used alone or in combination of two or more.

  These thermosetting resins may contain other components such as a curing agent, an inorganic filler, a curing accelerator, a coupling agent, and an inorganic flame retardant at the time of use. By doing so, it becomes possible to appropriately prepare a low dusting powder suitable for various usage methods depending on the difference in properties required for the low dusting powder resin mixture.

(Liquid paraffin)
The liquid paraffin contained in the low dusting powder according to the present embodiment is not particularly limited, but preferably contains an alicyclic component. Liquid paraffin containing an alicyclic component can be easily mixed uniformly with a thermosetting resin, and can be more excellent in suppression of dust generation during use.

  In addition, as described in Patent Document 3, liquid paraffin has been known to be used as a lubricant in combination with a thermoplastic resin. However, liquid paraffin is not used in combination with a thermosetting resin.

(Production method of low dusting powder)
The low dusting powder according to this embodiment is manufactured by mixing a thermosetting resin and liquid paraffin.

  Hereinafter, the manufacturing method according to the present embodiment will be described in detail.

The low dusting powder according to the present embodiment is manufactured, for example, by the following method.
First, liquid paraffin is mixed with the thermosetting resin. As a specific mixing method, a method of adding liquid paraffin to the molten thermosetting resin and stirring and mixing it is used. By doing so, liquid paraffin can be finely dispersed in the obtained low dusting powder.
Moreover, it is preferable that the mixing temperature of a thermosetting resin and a liquid paraffin is 80 degreeC or more and 250 degrees C or less. By mixing in this temperature range, the thermosetting resin and liquid paraffin are easily mixed uniformly.

  When mixing the thermosetting resin and the liquid paraffin, by mixing these components as uniformly as possible, it is possible to improve the degree of dust generation during use.

  The liquid paraffin to be added is preferably added in an amount of 0.05 to 2% by weight, more preferably 0.1 to 1% by weight, based on the total weight of the thermosetting resin. . When the amount of liquid paraffin added is within this range, the degree of suppression of dust generation when using the produced low dust generation powder can be further improved.

  Next, the obtained mixture of thermosetting resin and liquid paraffin is pulverized to obtain the low dusting powder according to the present embodiment.

  The resin composition that has been pulverized and powdered has a different particle diameter, but uniform electrostatic interaction can be caused by using a sieve to make the particle diameter uniform. By adjusting the particle diameters in this way, it is possible to further improve the degree of dust generation when using low dust generation powder. The preferable range of the particle diameter is as described above.

[Example]
(1) Production of low dusting powder First, 1000 parts by weight of phenol resin (Sumilite Resin (registered trademark) PR-50731 manufactured by Sumitomo Bakelite Co., Ltd.) in a 3 L cylindrical separable flask was heated to 200 ° C. And melted. In addition, the cylindrical separable flask used here uses what was equipped with the stirring apparatus, the reflux condenser, and the thermometer.

  Next, 2 parts by weight of liquid paraffin (MORESCO White P-350P manufactured by MORESCO) was added to the total weight of the molten phenol resin, and the mixture was stirred and mixed at 200 ° C.

  Next, the melt-mixed resin was taken out into a stainless steel vat and cooled at 25 ° C. (room temperature) to obtain a solid resin. Then, the obtained solid resin was pulverized with a ball mill until the average particle size became 30 μm to prepare a powder.

(2) Evaluation method and results The prepared powder was weighed out in a 100 cc plastic cup and dropped from 1 m above the ground at 25 ° C. Even when the powder thus produced was dropped, dust generation was hardly generated.

[Comparative example]
In the production of the powder of the example, the powder of the comparative example was produced without adding liquid paraffin. The evaluation was performed in the same manner as in the example.

  As a result, the produced powder generated intense dust.

In this way, by mixing liquid paraffin with the thermosetting resin, it is possible to obtain a powder that is superior in suppressing dust generation during use as compared with conventional thermosetting resins.
And the resin mixture was obtained by dry-mixing a filler with respect to the obtained powder. At this time, the powder obtained in the example hardly generated dust when dry-mixed with the filler. On the other hand, the powder resin composition obtained in the comparative example generated intense dust.

  As mentioned above, although embodiment of this invention was described, these are illustrations of this invention and various structures other than the above are also employable.

Claims (14)

Preparing a low dusting powder containing a thermosetting resin and liquid paraffin;
A step of dry-mixing the low dusting powder and the filler to obtain a low dusting powder resin mixture;
A method for producing a low dust-generating powder resin mixture.   The method for producing a low dusting powder resin mixture according to claim 1, wherein the thermosetting resin is a phenol resin or an epoxy resin.   The manufacturing method of the low dust generation powder resin mixture of Claim 1 or 2 in which the said liquid paraffin contains the alicyclic component.   4. The liquid paraffin according to claim 1, wherein 0.05% by weight to 2% by weight of the liquid paraffin is added to the total weight of the thermosetting resin in the step of preparing the low dusting powder. The manufacturing method of the low dust generation powder resin mixture as described in 1 above. A low dust generation powder used in the method for producing a low dust generation powder resin mixture according to claim 1,
A thermosetting resin;
Liquid paraffin,
Low dusting powder containing.   The low dusting powder according to claim 5, wherein the thermosetting resin is a phenol resin or an epoxy resin.   The low dusting powder according to claim 5 or 6, wherein the liquid paraffin contains an alicyclic component.   The low dust generation powder according to any one of claims 5 to 7, comprising 0.05% by weight or more and 2% by weight or less of the liquid paraffin with respect to the total weight of the thermosetting resin.   A method of reducing resin dust generation, which reduces the amount of dust generated by adding liquid paraffin to a molten thermosetting resin.   The method for reducing dust generation of a resin according to claim 9, wherein 0.05% by weight or more and 2% by weight or less of the liquid paraffin is added to the total weight of the thermosetting resin.   The manufacturing method of a molded article including the process of obtaining a molded article from the low dust generation powder resin mixture obtained by the manufacturing method of the low dust generation powder resin mixture as described in any one of Claims 1 thru | or 4.   The method for producing a molded product according to claim 11, wherein in the step of obtaining the molded product, the low-dusting powder resin mixture is heat-kneaded.   The method for producing a molded product according to claim 11, wherein in the step of obtaining the molded product, the low dusting powder resin mixture is melt-molded.   The method for producing a molded product according to claim 11, wherein in the step of obtaining a molded product, the low dusting powder resin mixture is applied to a substrate.