JP6604422B2 - Scale-like glass granules and method for producing the same - Google Patents

Description

The present invention relates to a scaly glass granule to be blended with a thermoplastic resin. Furthermore, it is related with the resin composition containing a scaly glass body, and its manufacturing method. The scaly glass body is also called glass flake or flaky glass.

The scale-like glass body produced by controlling to an appropriate thickness is not limited to thermoplastic resins, thermosetting resin reinforcements, anticorrosion lining fillers, etc., but also to paints, inks, cosmetics, etc. Widely used in applications that give unique sensitivity.
A scaly glass body is obtained by crushing a glass film controlled to an appropriate thickness into a scaly shape. A scaly glass granule is obtained by spraying a granulating agent containing a binder or the like to form a scaly glass body. Granulated into granules.
According to Patent Documents 1 and 2, the process of molding a thermoplastic resin using a scaly glass body or the like as a reinforcing material is as follows. First, a thermoplastic resin, a reinforcing material, an additive, and the like are mixed in a premixer such as a ribbon blender, and then melt-mixed using a melt-kneading apparatus such as an extruder, and then obtained by melt-kneading. The material is processed into a pellet by a pelletizer or the like. A desired molded body is obtained from the pellets by a method such as injection molding, extrusion molding, compression molding or rotational molding.
Generally, glass fiber is widely used as a reinforcing material for thermosetting resin (hereinafter, the thermoplastic resin to be reinforced is sometimes referred to as “matrix resin”).
However, since the glass fiber has directionality, for example, after glass fiber and a thermoplastic resin are blended and melt-kneaded with an extruder and pelletized, when producing a plate-shaped molded product with an injection molding machine, There was a defect that warpage and anisotropy of the linear expansion coefficient (difference in the ratio of the linear expansion coefficient in the resin flow direction and the direction perpendicular thereto) occurred in the molded product.
In order to solve this problem, a scaly glass body has been used as a reinforcing material. For example, Patent Document 3 discloses a method for producing a resin composition in which glass flakes alone or a resin blended with reinforcing fillers such as glass flakes and glass fibers is extruded and kneaded to form pellets as a reinforcing material. .

Patent Document 4 discloses a method for producing a resin composition in which a glass flake granulated into a granule with a binder is extruded and kneaded with a resin used for blending preparation.

Further, Patent Document 5 discloses a flaky glass granule in which a work having a low scattering degree and a low compression degree, in which a flaky glass is weakly aggregated with a binder containing a silane coupling agent and a resin, is improved.

Furthermore, Patent Document 6 discloses a method for producing granule flakes that are granulated using water or a volatile organic solvent without using a binder or a surface treatment agent.
Further, in Patent Document 7, granular glass flakes granulated with a binder containing a surfactant, a silane coupling agent, an epoxy resin and a urethane resin are not clogged or poorly bited in the feed part of an extrusion molding machine. It is disclosed that occurrence can be prevented.

JP 2002-146204 A JP 2008-74927 A Japanese Patent Laid-Open No. 62-109855 Japanese Patent Laid-Open No. 3-86753 JP 2006-152198 A WO2009 / 044866 JP 2003-82260 A

When a scale-like glass body is used for the reinforcing material, the warpage of the molded product and the anisotropy of the linear expansion coefficient are reduced, and the quality of the molded product is improved. There was a problem of clogging at the feed part to the machine, biting failure, etc. (Patent Document 1).

In addition, even when using scaly glass granules obtained by granulating scaly glass bodies, clogging in the feed section and improvement of poor biting are insufficient, and scattering of granular glass flakes In some cases, the strength of the resin molded product is unstable and the strength is not always increased even if the property is suppressed and the occurrence of troubles in supply to the extruder is reduced (Patent Documents 2 to 4).

In view of this, the present invention is to prepare the glassy glass granules, which are granulated from the glassy glass bodies, with the matrix resin, and to prevent the supply to the extruder when melt-kneading with the extruder. It aims at improving the tensile strength of the resin molded product obtained by reducing and improving the function as a reinforcing material of a scaly glass granule.

As a result of intensive studies by the present inventors, it is possible to granulate a scaly glass body with a granulating agent containing a predetermined amount of a surfactant to form a granular state, that is, a scaly glass granule. Then, it was found that the strength, particularly the tensile strength, of the molded product obtained can be improved by molding a thermoplastic resin obtained by melt-kneading with an extruder and dispersing the scaly glass granules.

In Patent Document 7, there is a description of granular glass flakes in which 0.1 to 2% by mass of a binder containing 0.01 to 1% by weight of a surfactant as a solid content with respect to the total solid content weight, and resin and Extrusion-kneading and molding into a desired shape by injection molding or the like, but the strength of the resin molded product is sometimes unstable and low. However, the inventor surprisingly found that the scaly glass granules obtained by adding more surfactant and containing 1.5 to 16% by mass of the solid content have a reduced scattering property. It was found that the strength physical properties of the molded product after molding such as injection molding are high and stable without causing clogging at the feed portion to the extruder and poor biting.

That is, the present invention is a thermoplastic resin composition comprising a matrix resin and scaly glass granules blended in the matrix resin,
The scaly glass granules are scaly glass granules obtained by coating and coating a scaly glass body with a granulating agent containing a resin, a surfactant and a silane coupling agent, and the resin is an epoxy resin or a urethane resin. And
The surfactant is any one of anion, cation, amphoteric or nonion, or a combination of two or more thereof.
In terms of solid content based on the granulating agent, the surfactant is contained in an amount of 3% by mass or more and 16% by mass or less, and the mass of the coating film of the granulating agent coated and coated on the scaly glass body is as described above. It is 0.1 mass% or more and 2 mass% or less on the basis of the total amount of scaly glass granules.
In the present invention, a film of silica (SiO ₂ ), metal and / or metal oxide is formed on the surface of the scale-like glass body.
Moreover, this invention is a thermoplastic resin composition containing the said scaly glass granule.
Moreover, this invention is a molded article which consists of said thermoplastic resin composition.
Furthermore, this invention is a manufacturing method of the thermoplastic resin composition containing the reinforcing material characterized by mix | blending and preparing the said scaly glass granule with a matrix resin, and melt-kneading with an extruder.
Further, the present invention is the above-mentioned production method, characterized in that a thermoplastic resin composition melt-kneaded and pelletized is injection-molded.

The scaly glass granules of the present invention have high dispersibility in a thermoplastic resin, feedability to an extruder, etc., can enhance the function as a reinforcing material, and increase the strength of the resulting resin molded product be able to.

It is a schematic sectional drawing of an example of an extruder.

Hereinafter, embodiments for carrying out the present invention will be described in detail.

The present invention is a scaly glass granule formed by coating and coating a scaly glass body with a granulating agent containing a resin, a surfactant and a silane coupling agent, the resin being an epoxy resin or a urethane resin, In terms of solid content based on the granules, the surfactant is contained in an amount of 3% by mass to 16% by mass, and the mass of the granule coating film contained in the flaky glass granules is the total amount of the flaky glass granules. It is a scale-like glass granule which is 0.1 mass% or more and 2 mass% or less on the basis. Hereinafter, each component requirement is demonstrated.
1. Regarding the glass, the glass species constituting the scaly glass body of the present invention is not particularly limited, and examples thereof include E glass, C glass, soda lime glass, and the like. A glass body is obtained.

The scale-like glass body of the present invention preferably has an average particle diameter (simple average of the longest diameter) of 10 to 3,000 μm in consideration of dispersibility in the thermoplastic resin. If it is smaller than 10 μm, it will hardly function as a reinforcing material, while if it is larger than 3,000 μm, the dispersibility in the thermoplastic resin will decrease. More preferably, it is 20-2,000 micrometers.

Moreover, as for the thickness of the scale-like glass body of this invention, 0.5-20 micrometers is preferable. If it is smaller than 0.5 μm, it is difficult to produce a scaly glass body, which is not practical. On the other hand, scaly glass bodies larger than 20 μm are clogged with a gate in a mold having a thin gate for molding fine parts during injection molding, causing trouble.

Moreover, it is preferable that the aspect-ratio (average particle diameter / average thickness) of the scale-like glass body of this invention is 2-1,000. When the aspect ratio is less than 2, the granule is not sufficiently large even if granulated, and the problem of scattering property and clogging at the feed portion is not improved. On the other hand, if it exceeds 1,000, the dispersibility is lowered, so that it is necessary to add a large amount of a surfactant, which may deteriorate the physical properties of the thermoplastic resin.

Moreover, the scaly glass body of the present invention may be provided with a metal and / or metal oxide thin film on its surface. The flaky glass body may contain a considerable amount of alkali metals and alkaline earth metals (hereinafter collectively referred to as “alkali components”) as a composition component. Alkali components are eluted, resulting in problems such as lowering the adhesive force between the thermoplastic resin and the glass flakes and causing discoloration. Therefore, by providing a thin film made of, for example, silica (SiO ₂ ) in advance on the surface of the scaly glass body, the elution of the alkali component can be suppressed and the occurrence of the above problem can be prevented.
Moreover, if the thickness of the thin film is adjusted to an integral multiple of 1/4 of the target visible light wavelength, it will exhibit a reflection interference color, so that the appearance of the resin composition has a desired color tone. Can be granted. Furthermore, if a metal thin film is provided on the surface of the scaly glass body, the gloss specific to the metal can be imparted to the scaly glass body, so that the appearance of the resin composition can be varied.
2. Regarding the granulating agent, the granulating agent applied to the flaky glass body of the present invention includes a silane coupling agent, a resin, a surfactant, and the like, and the solid content of the surfactant with respect to their total solid mass. Content rate ((solid content mass of surfactant / total solid content mass of granulating agent) × 100) is 1.5 to 16 mass%.

When the content is less than 1.5% by mass, the scaly glass bodies are poorly slidable, that is, the frictional force between the scaly glass bodies is large, and when blended with a thermoplastic resin, it is fed to an extruder. This causes clogging at the part, poor biting, etc., and dispersibility in the thermoplastic resin decreases. In addition, a composite with a thermoplastic resin has unstable strength properties. On the other hand, when the content exceeds 16% by mass, the cohesive force of the granulating agent is reduced, so that the feed property such as the mixture of the scaly glass body and the thermoplastic resin pellets is liable to stagnate in the feed portion of the extruder. . In addition, the presence of an excessive surfactant inhibits adhesion between the glass flakes and the thermoplastic resin. As for the content rate of solid content of surfactant, 3-12 mass% is more preferable.
[Surfactant]
The surfactant imparts great slipperiness and fluidity to the scaly glass body in order to reduce the frictional force between the scaly glass bodies. Therefore, the glass flakes obtained by granulating with a granulating agent containing a predetermined amount of surfactant are clogged at the feed section to the extruder and poorly bite when blended with a thermoplastic resin. Does not cause etc. Further, since the wettability between the glass flakes and the thermoplastic resin is improved, the glass flakes can be uniformly dispersed in the thermoplastic resin, and the strength of the thermoplastic resin molded product is stabilized. This surfactant is not limited to any one of anion, cation, amphoteric or nonionic.

The anionic surfactant is not particularly limited, but is sodium dioctyl sulfosuccinate, fatty acid salt, alkyl sulfate ester salt, alkyl sulfonate salt, alkyl aryl sulfonate salt, alkyl naphthalene sulfonate salt, alkyl sulfosuccinate. Examples thereof include acid salts, alkyl diphenyl ether disulfonates, alkyl phosphates, polyoxyethylene alkyl sulfate salts, polyoxyethylene alkyl allyl sulfate salts, and sulfosuccinate ester salts. In particular, sodium dialkylsulfosuccinate, which is generally used and easily available and has cost advantages, can be suitably used, and can be obtained as Perex OT-P (manufactured by Kao Corporation, solid content: 70% by mass).

Although it does not specifically limit as a cationic surfactant, A higher amine halogenate, a halogenated alkyl pyridinium, a quaternary ammonium salt, etc. are mentioned. In particular, butadiene maleic acid copolymer ammonium salt, which is widely used, easily available, and advantageous in terms of cost, can be suitably used. Acroresin BG-7 (manufactured by Sanyo Chemical Co., Ltd., solid content: 25% by mass) Available as
The amphoteric surfactant is not particularly limited, and examples thereof include alkylbendine. In particular, amidopropyl betaine laurate, which is widely used, easily available, and advantageous in terms of cost, can be suitably used, and it can be obtained as Amhitoal 20AB (manufactured by Kao Corporation, solid content 30% by mass).
The nonionic surfactant is not particularly limited, but polyoxyethylene glycol alkyl ethers such as polyoxyethylene lauryl ether, polyoxyethylene higher alcohol ether, polyoxyethylene octylphenyl ether, polyethylene glycol monostearate Polyethylene glycol fatty acid esters such as sorbitan monolaurate, sorbitan fatty acid esters such as polyoxyethylene sorbitan monolaurate, glycol fatty acid esters such as glycol monostearate, fatty acid monoglycerides or oxyethylene styrenated phenyl ether, etc. Is mentioned. In particular, oxyethylene styrenated phenyl ether, which is widely used, easily available, and advantageous in terms of cost, can be suitably used. Neugen EA-197D (Daiichi Kogyo Seiyaku Co., Ltd., solid content concentration 60% by mass) Available as

Two or more of these may be used in combination.
Surfactant gives great slip to glassy glass body, gives big fluidity to glassy glass body, and is clogged in feed section to extruder when it is blended with thermoplastic resin, poor bite, etc. Does not cause. Further, the wettability between the scaly glass body and the thermoplastic resin is improved, the scaly glass body is given uniform dispersibility in the thermoplastic resin, and the strength of the thermoplastic resin molded product is stabilized.
However, usually, when these surfactants are added excessively to the granulating agent, the binding force between the glass flakes is hindered, and the glass flakes granulated and granulated easily break down. The surfactant polyoxyethylene styrenated phenyl ether has a low influence on binding force inhibition. Nonionic surfactants are easy to handle because they are stable for a long time without causing precipitation even when mixed with silane coupling agents or resin emulsions, which are components of other granulating agents.
[resin]
The resin in the granulating agent has a function of bonding the glass flakes together, and the component of the resin is not particularly limited. For example, as an organic resin component, methyl cellulose, carboxymethyl cellulose, starch Carboxymethyl starch, hydroxyethyl cellulose, hydroxypropyl cellulose, polyvinyl alcohol, acrylic resin, epoxy resin, phenol resin, vinyl acetate or urethane resin.

These resin components can be used as an aqueous emulsion or dissolved in an organic solvent.
Examples of the inorganic resin component include water glass, colloidal silica, colloidal alumina, and the like.
Among the resin components, epoxy resins and urethane resins are preferably used. The epoxy resin mainly contributes to the expression of adhesion between the scaly glass body and the thermoplastic resin. In particular, the epoxy equivalent (gram number of resin containing 1 gram equivalent of an epoxy group) is small, that is, the phenol novolac type having a high epoxy group concentration, for example, epoxy having an epoxy equivalent of 180 to 190 g / eq. As resin emulsions, trade names Epojon EA10, HC32, HC35 and HC78 manufactured by Henkel Japan KK can be obtained.
The urethane resin mainly contributes to the expression of the binding force between the scaly glass bodies. In particular, when a polyether is used as the polyol and a urethane resin obtained by polymerizing xylylene diisocyanate or isophorone diisocyanate is used as the diisocyanate, the thermoplastic resin molded body reinforced with the scaly glass body is hardly yellowed and has a water resistance. Do not decrease. For example, trade name Yodosol RC32 manufactured by Henkel Japan KK can be obtained as an emulsion of urethane resin polymerized with polyether and xylylene diisocyanate.
[Silane coupling agent]
The silane coupling agent is an organosilicon compound having two or more types of reactive groups in the molecule, one of which reacts with the surface of the glass flake and the other reactive group is an organic resin component and thermoplastic. Since it reacts with the resin, the familiarity between the scaly glass body and the thermoplastic resin can be improved.
As the silane coupling agent, aminosilane and / or epoxysilane is preferably used, and aminosilane is not particularly limited, but 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, N- ( 2-aminoethyl) -3-amino-arranged propyltrimethoxysilane, N- (2-aminoethyl) -3-aminopropylmethyldimethoxysilane, 3-triethoxysilyl-N- (1,3-dimethyl-butylidene) Preference is given to the hydrochlorides of propylamine, 3- (N-phenyl) aminopropyltrimethoxysilane and N- (vinylbenzyl) -2-aminoethyl-3-aminopropyltrimethoxysilane. In particular, 3-aminopropyltriethoxysilane, which is widely used, easily available, and advantageous in terms of cost, can be suitably used, and can be obtained as Silaace S330 (manufactured by Chisso Corporation, purity 98% by mass).
The epoxy silane is not particularly limited, but 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3- Glycidoxypropylmethyldiethoxysilane and 3-glycidoxypropyltriethoxysilane are preferred. In particular, 3-glycidoxypropyltrimethoxysilane, which is widely used, easily available, and advantageous in terms of cost, can be suitably used as KBM-403 (manufactured by Shin-Etsu Chemical Co., Ltd., purity 100% by mass). Available.
Two or more silane coupling agents may be used in combination.
Moreover, the said epoxy resin and urethane resin are familiar with the said silane coupling agent and a thermoplastic resin. If the epoxy resin, the urethane resin, and the silane coupling agent are used in combination, the scaly glass body can be firmly bonded to the thermoplastic resin and exhibit a sufficient function as a reinforcing material.
Although the content ratio in the granulated film of each component of the said epoxy resin, urethane resin, and the said silane coupling agent is not specifically limited, The solid content mass which combined the epoxy resin, urethane resin, and the silane coupling agent is based on 100% The epoxy resin is preferably 40 to 70% by mass, the urethane resin is 20 to 50% by mass, and the silane coupling agent is preferably 10 to 40% by mass. When the content ratio of the epoxy resin is too small, that is, the content ratio of the urethane resin is too large, the strength of the thermoplastic resin molded product is inferior or / and the thermoplastic resin molded product is easily colored. On the other hand, when the content ratio of the epoxy resin is excessive, that is, the content ratio of the urethane resin is excessively low, the melt viscosity of the thermoplastic resin at the time of injection molding is high, which causes trouble when molding a molded product having a fine shape or / and scales. The glass granules are easily broken and clogged at the feed section to the extruder, causing poor biting. When the content ratio of the silane coupling agent is too small, the strength of the thermoplastic resin molded article is inferior, and when it is excessive, that is, when the ratio is larger than 40% by mass, an increase in strength of the thermoplastic resin molded article cannot be expected.
[Granulating agent]
The concentration of the granulating agent is usually adjusted using water or alcohol as a solvent so that each component can uniformly exist on the surface of the glass flake. It is preferable that solid content is 1-10 mass% with respect to the total mass of the granulation agent containing a solvent. When the content is less than 1% by mass, the concentration is too low to allow the granulating agent to adhere sufficiently to the surface of the glass flakes. On the other hand, when the content exceeds 10% by mass, the concentration is high. Thus, it becomes difficult to adjust the adhesion rate of the desired granulating agent and to uniformly apply it to the surface of the scaly glass body. In addition to the silane coupling agent, the resin component, and the surfactant, known additives such as an antifoaming agent and an antistatic agent may be added to the granulating agent as long as the object of the present invention is not impaired.
The method for preparing the granulating agent is not particularly limited. After hydrolysis by adding a silane coupling agent to the solvent at room temperature and atmospheric pressure, a resin, a surfactant and the like are appropriately added to the solvent, Prepared by stirring until uniform.
A scaly glass body is coated with a granulating agent, granulated and dried to form a film. The adhesion rate of the film, that is, the mass percentage of the film with respect to the scaly glass granules coated and dried with a granulating agent is 0.1 to 2% by mass.

When this adhesion rate is less than 0.1% by mass, the bonding force between the scaly glass bodies is weak, so that the granule obtained by granulating the scaly glass body tends to collapse. On the other hand, if it exceeds 2% by mass, the dispersibility of the glass flakes in the thermoplastic resin deteriorates during kneading in the extruder. Furthermore, the granulating agent film is decomposed during injection molding, and a large amount of gas is generated to cause contamination of the mold, or the resin composition may be discolored.

The method for granulating the scaly glass body is not particularly limited, and can be granulated by a known means. For example, stirring granulation method, fluidized bed granulation method, spray granulation method, rotary granulation method and the like. Specifically, a scaly glass body to which an appropriate amount of a granulating agent is adhered using a spray or the like is spread on a rotating drum or on a vibrating tray and applied while evaporating the solvent by heating.
3. As the thermoplastic resin composition, the thermoplastic resin is not particularly limited. For example, polyethylene, polypropylene, polyvinyl chloride, polystyrene, AS resin, ABS resin, polyethylene terephthalate, methacrylic resin, polycarbonate, polyamide, polyacetal. , Polybutylene terephthalate, amorphous polyarylate, polysulfone, polyethersulfone, polyphenylene sulfide, polyetheretherketone, polyetherimide, liquid crystal polymer, and fluorine resin.
4). Melting and kneading by an extruder The scaly glass body is melt-kneaded using an extruder and uniformly dispersed in a thermoplastic resin, pelletized, or extruded into a long product as it is. The pellets of the thermoplastic resin composition containing the scaly glass granules thus produced may be molded into a desired shape by injection molding or the like.
The extruder to be used is not particularly limited. As the extruder, a single-screw extruder composed of a pair of cylinders and screws, or a twin-screw extruder composed of two pairs of cylinders and screws arranged in parallel is widely used. Extruders are used to melt and knead thermoplastic resins, reinforcing materials (such as glass flakes and glass fibers), and other additives to produce pellets, or to take long objects with fixed cross-sectional shapes such as pipes and rods. Used when manufacturing continuously.
FIG. 1 shows a schematic diagram of a single-screw extruder as an example of an extruder. The thermoplastic resin, the reinforcing material and other additives are mixed in advance by the premixer and charged into the hopper of the extruder. Of a thermoplastic resin, a reinforcing material, and other additives with a cylinder and a screw that are heated in advance to a predetermined temperature (a temperature that is 50 to 150 ° C. higher than the melting point of the thermoplastic resin or the glass point transition temperature so that sufficient fluidity can be obtained). The mixture is melt kneaded and extruded from a die. The string-like molten mixture extruded from the die is cooled with water or the like and cut with a pelletizer to form a master batch. When extruding a long product with a fixed cross-sectional shape such as a pipe or a bowl, the melt-kneaded material extruded from the die is continuously drawn and cooled to obtain a molded product by cutting it to a predetermined length. . The shape of the extrusion port of the die is a circle with a diameter of several millimeters at the time of pellet production. The one with the shape of the extrusion opening is used.

As for the content rate of the scaly glass body in a thermoplastic resin composition, 5-70 mass% is preferable. When it is less than 5% by mass, the function as a reinforcing material is not sufficiently exhibited. On the other hand, when it exceeds 70 mass%, uniform dispersion in the thermoplastic resin composition becomes difficult.

In addition, the thermoplastic resin composition may contain a reinforcing material other than the scaly glass body such as glass fiber depending on the application. For example, in applications of electrical appliances and electronic equipment parts, since extremely high strength is required, it is preferable to mix glass fibers in the same amount as that of the scaly glass body.

5. Strength of molded product of thermoplastic resin composition The strength of the molded product of the thermoplastic resin composition is evaluated by a tensile test method based on JIS K7113 or ASTM D-638. If the matrix resin and the reinforcing material are the same, the ease of wetting of the reinforcing material by the matrix resin and the dispersibility of the reinforcing material in the matrix resin appear in the tensile strength. The easier the wetting of the reinforcing material to the matrix resin and the better the dispersibility of the reinforcing material in the matrix resin, the greater the tensile strength. The ease of wetting by the matrix resin of the glass flakes of the present invention and the dispersibility of the glass flakes in the matrix resin are determined by the coating film covering the glass flakes of the present invention, that is, the composition of the granulating agent. It is greatly affected. Therefore, by adjusting the composition of the granulating agent, the tensile strength of the thermoplastic resin molded product obtained by melt-kneading the scaly glass granules coated with the granulating agent and dried to form a coating, that is, the molded product The strength of can be improved.

Hereinafter, the present invention will be described in detail by way of examples and comparative examples.

The scaly glass granules obtained in this example and the comparative example were evaluated by the following method.
<Loss on ignition>
It is how to express the coating amount of the granulating agent adhering to the scaly glass granules.

The mass change rate after heating the scaly glass granules at 600 ° C. for 20 minutes is expressed with reference to the scaly glass granules before heating. The formula is (solid content adhesion rate of granulating agent, mass%) = (mass change amount of scaly glass granules before and after heating) / (mass of scaly glass granules before heating).
<Feed properties>
Compounded at a ratio of 40 parts by weight of glass flakes and 100 parts by weight of ABS resin, put into a hopper of an extruder (model V-USV, manufactured by Union Plastics Co., Ltd.), and blended with glass flakes and ABS resin The feeding (feeding) property to the extruder was observed. “X” when the flow of the compound is stagnated even once, and the supply to the extruder is hindered, and “○” when there is no hindrance in the flow of the compound and there is no hindrance to the supply to the extruder .
<Dispersibility of flaky glass in matrix resin>
The scaly glass granules obtained here were blended in a thermoplastic resin, and the dispersibility thereof was measured. Using an extruder (Union Plastic Co., Ltd., model V-USV), 40 parts by mass of flaky glass granules and 100 parts by mass of ABS resin were blended to form pellets.
When this pellet was observed with a soft X-ray photograph, in Examples 1 to 6, no lump of scaly glass body was observed, and it was confirmed that the scaly glass body was uniformly dispersed throughout. In this observation, the dispersibility was evaluated by the number of flaky glass masses present in 500 pellets. “5” when no flaky glass body lump is present, “4” when one, “3” when two, “2” when three, “1” when four or more It was.
<Tensile strength>
Further, the pellets were injection molded using an injection molding machine (manufactured by Nissei Plastic Industry Co., Ltd., model FS80S12A arrangement SE), and a tensile strength test (according to ASTM D-638: measurement temperature 23 ° C.) was performed. It was.

As described above, the granule composition, the solid content of the granule, the loss on ignition, the feed property, the dispersibility, and the tensile strength of Examples 1 to 6 and Comparative Examples 1 to 4 are summarized in Table 1.

Example 1
(Preparation of granulating agent)
Using water as a solvent, 3-aminopropyltriethoxysilane (B) (manufactured by Chisso Corporation, trade name: Silaace S330, purity: 98% by mass), polyether urethane resin (C) emulsion (trade name, manufactured by Henkel Japan Co., Ltd.) Yodozol RC32, solid content concentration 31% by mass), phenol novolac type epoxy resin (D) emulsion (trade name Epochon HC35, solid content concentration 50% by mass, manufactured by Henkel Japan Ltd.) and nonionic surfactant polyoxyethylene styrenation A granulating agent containing phenyl ether (A1) (Daiichi Kogyo Seiyaku Co., Ltd., Neugen EA-197D, solid content concentration 60 mass%) was prepared.
The content ratio of each component of the granulating agent is expressed as a mass percentage based on 100% of the solid content mass of (B), (C), (D), and (A1). (B) is 24.3% by mass, (C) is 31.6% by mass, (D) is 42.6% by mass, and (A1) is 1.5% by mass. In addition, each mass of said (B), said (C), said (D), and said (A1) in a granulation agent was calculated | required by converting into solid content from each solid content density | concentration. The mass of (B) was determined as an unhydrolyzed product.
The solid content of the granulating agent was 4.1% by mass.
(Granulation of scaly glass body)
The above granulating agent was applied to a scaly glass body (having no metal thin film or the like) of E glass composition having an average particle diameter of 140 μm and an average thickness of 5 μm by using a spray, and placed in a polyethylene bag. The polyethylene bag was inflated with air, sealed, shaken and granulated, then removed from the polyethylene bag and dried with a hot air dryer to obtain scaly glass granules. The solid content adhesion rate of the granulating agent was 0.6% by mass with loss on ignition.
Example 2
In the composition of Example 1, the content ratio of each component is expressed as a mass percentage based on 100% of the solid content mass of the (B), the (C), the (D), and the (A1). The (B) was 24.0% by mass, the (C) was 31.1% by mass, the (D) was 41.9% by mass, and the (A1) was 3.0% by mass, A granulating agent was prepared in the same manner as in Example 1.
The solid content of the granulating agent was 4.2% by mass.
(Granulation of scaly glass body)
The scaly glass body was the same as that used in Example 1, and the same operation as in Example 1 was performed to obtain scaly glass granules. The solid content adhesion rate of the granulating agent was 0.6% by mass with loss on ignition.
Example 3
(Preparation of granulating agent)
In the composition of Example 1, the content ratio of each component is expressed as a mass percentage based on 100% of the solid content mass of the (B), the (C), the (D), and the (A1). The (B) was 22.4% by mass, the (C) was 29.1% by mass, the (D) was 39.1% by mass, and the (A1) was 9.4% by mass, A granulating agent was prepared in the same manner as in Example 1.
The solid content of the granulating agent was 4.5% by mass.
(Granulation of scaly glass body)
The scaly glass body was the same as that used in Example 1, and the same operation as in Example 1 was performed to obtain scaly glass granules. The solid content adhesion rate of the granulating agent was 0.6% by mass with loss on ignition.

Example 4
(Preparation of granulating agent)
In the composition of Example 1, the content ratio of each component is expressed as a mass percentage based on 100% of the solid content mass of the (B), the (C), the (D), and the (A1). The (B) was 21.7% by mass, the (C) was 28.3% by mass, the (D) was 38.0% by mass, and the (A1) was 12.0% by mass, A granulating agent was prepared in the same manner as in Example 1.
The solid content of the granulating agent was 4.5% by mass.
(Granulation of scaly glass body)
The scaly glass body was the same as that used in Example 1, and the same operation as in Example 1 was performed to obtain scaly glass granules. The solid content adhesion rate of the granulating agent was 0.6% by mass with loss on ignition.

Example 5
(Preparation of granulating agent)
In the composition of Example 1, the content ratio of each component is expressed as a mass percentage based on 100% of the solid content mass of the (B), the (C), the (D), and the (A1). The (B) is 20.7% by mass, the (C) is 27.0% by mass, the (D) is 36.3% by mass, and the (A1) is 16.0% by mass, A granulating agent was prepared in the same manner as in Example 1.
The solid content of the granulating agent was 4.6% by mass.
(Granulation of scaly glass body)
The scaly glass body was the same as that used in Example 1, and the same operation as in Example 1 was performed to obtain scaly glass granules. The solid content adhesion rate of the granulating agent was 0.6% by mass with loss on ignition.

Example 6
(Preparation of granulating agent)
In the composition of Example 3, 9.4% by mass of (A1) was replaced with 9.4% by mass of Perex OT-P (manufactured by Kao Corporation, solid content of 70% by mass) (A2) as sodium dialkylsulfosuccinate. Except for the above, a granulating agent was prepared with the same composition and the same operation as in Example 3.
The solid content of the granulating agent was 4.2% by mass.
(Granulation of scaly glass body)
The scaly glass body was the same as that used in Example 1, and the same operation as in Example 1 was performed to obtain scaly glass granules. The solid content adhesion rate of the granulating agent was 0.6% by mass with loss on ignition.
Example 7
(Preparation of granulating agent)
In the composition of Example 3, 9.4% by mass of the above (A1) was used as an butadiene maleic acid copolymer ammonium salt as an acroresin BG-7 (manufactured by Sanyo Chemical Co., Ltd., solid content 25% by mass) (A3) 9. A granulating agent was prepared by the same composition and the same operation as in Example 3 except that the amount was changed to 4% by mass.
The solid content of the granulating agent was 4.2% by mass.
(Granulation of scaly glass body)
The scaly glass body was the same as that used in Example 1, and the same operation as in Example 1 was performed to obtain scaly glass granules. The solid content adhesion rate of the granulating agent was 0.6% by mass with loss on ignition.
Example 8
(Preparation of granulating agent)
In the composition of Example 3, the above (A1) 9.4% by mass was changed to Amphithol 20AB (manufactured by Kao Corporation, solid content 30% by mass) (A4) 9.4% by mass as amidopropyl betaine laurate. Prepared a granulating agent with the same composition and the same operation as in Example 3.
The solid content of the granulating agent was 4.4% by mass.
(Granulation of scaly glass body)
The scaly glass body was the same as that used in Example 1, and the same operation as in Example 1 was performed to obtain scaly glass granules. The solid content adhesion rate of the granulating agent was 0.6% by mass with loss on ignition.
Comparative Example 1
(Preparation of granulating agent)
In the composition of Example 1, except for (A1), the content ratio of each component is expressed as a mass percentage based on 100% of the solid content of the above (B), (C) and (D). The same operation as in Example 1 was conducted except that (B) was 24.7% by mass, (C) was 32.1% by mass, and (D) was 43.2% by mass. To prepare a granulating agent.
The solid content of the granulating agent was 4.1% by mass.
(Granulation of scaly glass body)
The scaly glass body was the same as that used in Example 1, and the same operation as in Example 1 was performed to obtain scaly glass granules. The solid content adhesion rate of the granulating agent was 0.6% by mass with loss on ignition.
Comparative Example 2
(Preparation of granulating agent)
In the composition of Example 1, the content ratio of each component is expressed as a mass percentage based on 100% of the solid content mass of the (B), the (C), the (D), and the (A1). The (B) was 24.4% by mass, the (C) was 31.7% by mass, the (D) was 42.6% by mass, and the (A1) was 1.3% by mass, A granulating agent was prepared in the same manner as in Example 1.
The solid content of the granulating agent was 4.3% by mass.
(Granulation of scaly glass body)
The scaly glass body was the same as that used in Example 1, and the same operation as in Example 1 was performed to obtain scaly glass granules. The solid content adhesion rate of the granulating agent was 0.6% by mass with loss on ignition.
Comparative Example 3
(Preparation of granulating agent)
In the composition of Example 1, the content ratio of each component is expressed as a mass percentage based on 100% of the solid content mass of the (B), the (C), the (D), and the (A1). The (B) was 20.4% by mass, the (C) was 26.6% by mass, the (D) was 35.8% by mass, and the (A1) was 17.2% by mass, A granulating agent was prepared in the same manner as in Example 1.
The solid content of the granulating agent was 4.5% by mass.
(Granulation of scaly glass body)
The scaly glass body was the same as that used in Example 1, and the same operation as in Example 1 was performed to obtain scaly glass granules. The solid content adhesion rate of the granulating agent was 0.6% by mass with loss on ignition.
Comparative Example 4
No granulating agent was applied.

As shown in the results of Examples 1 to 8 which fall within the technical category of the present invention, the surfactant is included in the granulated film of the glass flakes at a solid content ratio of 1.5 to 16% by mass. When the mixture of scale-like glass granules and ABS resin pellets was put into a hopper of an extruder, the feedability was good. Furthermore, the dispersibility of the scaly glass body in the pellets obtained by melt-kneading the compound with an extruder is good, and the tensile strength of the test piece injection-molded with the pellets is a technical category of the present invention. It was stable at a high value as compared with Comparative Examples 1 to 4 deviating from the above.

On the other hand, Comparative Examples 1 to 4 deviating from the technical category of the present invention were inferior to Examples 1 to 8 entering the technical category of the present invention in all of feedability, dispersibility, and tensile strength.

Paying attention to Example 1 and Comparative Example 2 and Example 5 and Comparative Example 3, the surfactant ratio was between 1.3% and 1.5% by weight and between 16.0% and 17.2% by weight. The difference in performance related to the feed property, dispersibility and tensile strength appears greatly, and it was found that the surfactant should be used in an amount of 1.5 to 16% by mass.

In Comparative Examples 1 and 2, the surfactant was not added and was too small, and the smoothness of the scaly glass granules was poor and the feedability was lowered. In addition, the improvement of the wettability between the glass flakes and the thermoplastic resin was insufficient and the dispersibility and tensile strength were poor.

The scaly glass granule of Comparative Example 3 was inferior in feedability because the granules were liable to collapse and there was no unity. Therefore, the dispersibility and tensile strength were also inferior. Moreover, it is estimated that the presence of excess surfactant inhibited the adhesion between the scaly glass body and the ABS resin.

Tensile strength is considered to be affected by the compatibility between the granulated film and the matrix resin. From the results of this example and the comparative example, the dispersibility of the glass flakes in the matrix resin is influenced by the feed property. Receive. Therefore, it is important to achieve both compatibility and feedability. For that purpose, it turned out that it is good to use surfactant between 1.5-16 mass% in a granulated film by solid content ratio.

DESCRIPTION OF SYMBOLS 1 Hopper 2 Screw 3 Cylinder 41-44 Heater 51-53 Cooling fan 6 Motor and transmission 7 Breaker plate 8 Die 9 Feed part

Claims (5)

A scaly glass granule formed by coating and coating a scaly glass body with a granulating agent containing a resin, a surfactant and a silane coupling agent,
The resin is an epoxy resin or a urethane resin,
The surfactant is any one of anion, cation, amphoteric or nonion, or a combination of two or more thereof.
Containing 1.5% by mass or more and 16% by mass or less of the surfactant in terms of solid content based on the granulating agent,
The mass of the film of the granulating agent coated and coated on the scaly glass body is 0.1% by mass or more and 2% by mass or less based on the total amount of the scaly glass granules.
Scaly glass granules. The scaly glass granule according to claim 1, wherein the surfactant is contained in an amount of 3% by mass to 12% by mass in terms of solid content based on the granulating agent. The surfactant is
Polyoxyethylene styrenated phenyl ether,
Sodium dialkylsulfosuccinate,
Butadiene maleic acid copolymer ammonium salt,
The scaly glass granule according to claim 1 or 2, which is either lauric acid amidopropyl betaine. The flaky glass granule according to any one of claims 1 to 3, wherein a film of silica (SiO ₂ ), metal and / or metal oxide is formed on the surface of the flaky glass body. A method for producing a scaly glass granule, comprising preparing a granulating agent containing a resin, a surfactant and a silane coupling agent, and coating and coating the granulating agent on the scaly glass body,
The resin is an epoxy resin or a urethane resin,
The surfactant is any one of anion, cation, amphoteric or nonion, or a combination of two or more thereof.
The granulating agent contains the surfactant in an amount of 1.5% by mass to 16% by mass in terms of solid content based on the granulating agent,
The mass of the film of the granulating agent coated and coated on the scaly glass body is 0.1% by mass or more and 2% by mass or less based on the total amount of the scaly glass granules.
A method for producing scaly glass granules.