WO2001027193A1

WO2001027193A1 - Thermoplastic-resin additive for matting and thermoplastic resin composition containing the same

Info

Publication number: WO2001027193A1
Application number: PCT/JP2000/007077
Authority: WO
Inventors: Takanobu Sakai; Hisakazu Hojo; Hidemitsu Kasahara; Katsuhiko Matsuo
Original assignee: Maruo Calcium Company Limited
Priority date: 1999-10-13
Filing date: 2000-10-12
Publication date: 2001-04-19
Also published as: KR20020037370A; TW555802B; KR100682755B1; JP4738687B2

Abstract

A thermoplastic-resin additive for matting comprising particles of heavy calcium carbonate which have irregular polyhedral shapes and have been regulated with respect to particle size and particle size distribution; and a thermoplastic resin composition containing the additive. The composition is excellent in matte properties, antiglare properties, and total light transmission and is useful in the fields of covers for lighting appliances, illuminated signboards, various displays, glazing, signs, etc.

Description

Technical Field Additive for thermoplastic resin for matting and thermoplastic resin composition containing the same

The present invention relates to a thermoplastic resin additive for matting, and a thermoplastic resin composition containing the additive.

For more details, see Lighting Covers, Lighting Signs, Various Displays, Grooming, Signs, etc. The present invention relates to a thermoplastic resin composition having excellent anti-glare property, anti-glare property and total light transmittance. Background art

In general, thermoplastic resin compositions substituted for (meth) acrylic resin, styrene resin, polycarbonate resin, polyester resin, vinyl chloride resin, or ABS resin are used for lighting fixture covers, lighting signs, and various discs. It is widely used for playing, grozing, and signing. In particular, in the application of lighting covers, so-called milky translucent plate-shaped products that have undergone secondary processing such as breath processing and vacuum processing have become widespread for the purpose of improving lighting efficiency and anti-glare effects inside cars. I have.

These milky white translucent plates are required to have not only anti-glare properties for protecting eyes from light sources, physical properties such as total light transmittance for efficiently producing illumination energy, but also excellent beauty and the like.

The above (meth) acrylic resin, styrene resin, polycarbonate resin, polyester resin for the purpose of imparting physical properties such as anti-glare properties and total light transmittance In addition, a method of adding inorganic particles such as barium sulfate or calcium carbonate, glass beads, or plastic to a vinyl chloride resin, an ABS resin, or the like as a light diffusing agent has been proposed and used.

For example, Japanese Patent Publication No. Hei 3-2188 discloses a method of adding calcium carbonate having a controlled particle size and shape, Japanese Patent Application Laid-Open No. 56-106237 discloses a method of adding glass beads, and Japanese Patent Application Laid-Open No. 2-6557 discloses a transparent plastic. And a method of adding glass beads has been proposed. They achieve the object by diffusing light from a light source with additives and imparting the desired total light transmittance and antiglare property to the above-mentioned resins.

However, the above-mentioned resin has a satiated surface, and when used for lighting covers or various displays used indoors or in vehicles, the presence or absence of 继 may determine the commercial value.

For example, in the case of lighting covers used in single-home households, personal preferences are prioritized, so many products require calm colors, and glossy resins are required.

In addition, the harmony between the lighting cover when the lights are turned off and the atmosphere in the room requires adjustment of the presence or absence of the gloss and the strength. In addition, the demand for the color tone caused by the gloss is strongly demanded not only for ordinary households but also for indoors such as hotels, exhibition halls, public halls, etc. due to their design.

Conventionally, the following two methods have been proposed as broadly divided methods for erasing the resin.

[1] Cresting process on resin surface. [2] A method of adding an inorganic or organic demulsifier to a resin.

The above method (1) has the advantage that the physical properties such as the impact resistance of the resin and the high elongation are small, but the productivity is poor and the processing cost is high, and the destructive effect is also insufficient. , Especially when secondary processing is applied, the erase effect that has been applied is significantly reduced It has the disadvantage that it disappears. In particular, when used for a lighting cover or the like, the above-mentioned secondary processing is often performed, which is not suitable in terms of imparting an erasing effect.

-On the other hand, the method of the above [2] has the advantage that the productivity does not decrease so much, the degree of deglazing can be controlled, and it can be applied to secondary processing applications. There is a risk that the physical properties of the material will be reduced.

For example, Japanese Patent Application Laid-Open No. 9-272777 reports that when an inorganic substance such as silica gel is used as an anti-glazing agent, physical properties such as impact resistance, elongation, and transparency are significantly reduced.

Further, as a method of using an organic substance, particularly a polymer-based matting agent, a method of using a crosslinked polymer having an average particle diameter of 35 to 500 / m obtained by suspension polymerization described in JP-A-56-36535 is known. No. However, the resin obtained by this method has a small decrease in the physical properties of the resin itself such as impact resistance and elongation, but has insufficient II-erasing effect, and the crosslinked polymer has a semi-crosslinked structure. Since it is united, it has a drawback that when it is shaped into a film, a bud is formed. In particular, when it is used for an acrylic resin and is shaped into a film, the transparency is significantly reduced, which is not preferable.

Japanese Patent Application Laid-Open No. 7-316374 discloses that in vinyl chloride resin, hydroxyalkyl methacrylate or hydroxyalkyl methacrylate having an alkyl group having a specific number of carbon atoms is used. In addition, a thermoplastic resin having an anti-glare property is obtained from a linear polymer having a hydroxyl group by other copolymerizable vinyl monomer, but it is not always satisfactory.

Japanese Patent Application Laid-Open No. 7-316389 discloses that an ABS resin having an alkyl group having a specific number of carbon atoms has an α-alkyl acrylate or a hydroxyalkyl ester of methacrylic acid. Alkyl acrylates and other copolymerizable vinyl monomers and hydroxyl-containing linear polymers have been used to obtain glossy thermoplastic resins, but their glossiness is not necessarily sufficient. It is hard to say.

Also, in Japanese Patent Application Laid-Open No. 7-314S15, an acrylic resin 'vinyl chloride resin-ABS resin is provided with acryl acrylate σ-quin alkyl ester having an alkyl group having a specific number of carbon atoms ■ methacrylic acid alkyl ester' alkyl acrylate ester ' A crosslinked polymer obtained by polymerizing a mixture of a noncrosslinkable monomer mixture composed of a vinyl aromatic monomer and other ethylenically unsaturated monomers and a crosslinkable polymer having two or more double bonds in a molecule. By laminating this on acryl resin, polycarbonate resin, vinyl chloride resin-ABS resin, etc., a thermoplastic resin with an anti-glare property is obtained, but the anti-erasing property is not necessarily sufficient.

Furthermore, by adding the method of the above [1] to the above method, the desired total light transmittance-anti-glare property * saturating property was obtained simply and inexpensively, but the variety of tastes was sufficiently satisfied. I couldn't do that.

Thus, (meth) acrylic resin, styrene resin, polycarbonate resin, polyester resin, vinyl chloride resin, ABS resin, etc. are used for lighting equipment covers, lighting signs, various displays, grooming, signs, etc. There has been a demand for a method of effectively imparting an anti-glare property while maintaining the total light transmittance of a thermoplastic resin and the anti-glare property.

The present invention relates to a (meth) acrylic resin, a styrene resin, a polycarbonate resin, a polyester resin, a vinyl chloride resin, an ABS resin, and the like, which are used for covers for lighting fixtures, lighting signs, various displays, gluing, signs, and the like. Total light transmittance of the thermoplastic resin 'Effectively imparts erasability without impairing the antiglare property 铯 6 Erasing thermoplastic resin additive, and blending the thermoplastic resin additive for erasing To provide a thermoplastic resin composition comprising: The porpose is to do. Disclosure of the invention

As a result of intensive studies, the inventors of the present invention have found that, by crushing and processing white saccharitic limestone and classifying it with high precision, heavy particles having an unspecified polyhedral shape and a specific abundance distribution are obtained. The present inventors have found that a thermoplastic resin additive for matting made of calcium carbonate can effectively impart a matting effect to a thermoplastic resin without impairing the total light transmittance and the antiglare property, and reached the present invention. That is, a first aspect of the present invention includes a thermoplastic resin additive for quenching, which is composed of heavy calcium carbonate and satisfies the particle size distribution structures of the following formulas (1) to (5) (claim 1).

2≤ A≤ 3 0 (1)

0≤B≤ 25 (2)

1 ≤ C≤ 2 5 (3)

1≤D≤ 3 (4)

E≤ 1 0 0 (5)

However,

A: Cumulative 50% diameter of heavy calcium carbonate passing through the sieve obtained by measurement with a laser flowmeter (Microtrac FRA) ίμτη

：: Cumulative percentage of heavy calcium carbonate obtained by measuring with a laser type flowmeter (Microtrac FRA) passing through the sieve passing through a sieve with a particle diameter 1/2 that is 50% of the cumulative passing side of the 50% sieve [%]

C: The value obtained by dividing the 90% cumulative diameter on the passing side of heavy calcium carbonate obtained by measuring with a laser set flowmeter (Microtrac FRA) by the 10% diameter [1]

D: Measured with a laser type flowmeter (Microtrac FRA) Value obtained by dividing the cumulative 75% diameter of the heavy carbon dioxide rusidium passing through the sieve by 25%

E: Maximum particle size of heavy calcium carbonate obtained by measurement with a laser type flowmeter (Microtrac FRA) [m]

In a preferred embodiment, the heavy-duty calcium carbonate is a thermoplastic additive for matting having a constant-pressure aerated powder specific surface area Sw in the range of 2,000 to 000 cm ² / g (Claim 2).

In a preferred embodiment, the additive is a 16-erasing thermoplastic resin additive obtained by surface-treating heavy calcium carbonate with 0.01 to 5 parts by weight of a hydrophobicity-imparting agent based on 100 parts by weight of heavy calcium carbonate (Claim 3).

In a preferred embodiment, the hydrophobic additive is a thermoplastic additive for extinguishing an iris, which is obtained by adding 0.01 to 5 parts by weight of a flow aid to 100 parts by weight of heavy calcium carbonate (Claim 4).

A second aspect of the present invention is directed to a thermoplastic resin composition characterized in that the above-mentioned thermoplastic resin additive for resting is blended with a thermoplastic resin.

In a preferred embodiment, the thermoplastic resin composition is such that the amount of the extinguishing thermoplastic resin additive is 0.5 to 5 parts by weight per 100 parts by weight of the thermoplastic resin (Claim 6).

A third aspect of the present invention is a thermoplastic resin composition comprising the thermoplastic resin additive and the light diffusing agent described above in combination with the thermoplastic resin (claim 7).

In a preferred embodiment, the light-diffusing agent is at least one selected from the group consisting of a synthetic calcium carbonate, a barium sulfate, a glass bead, and a sili force which satisfies the condition of the following formula (6). 8).

0.05≤ F≤10.0 (6) However,

F: Cumulative 50% diameter on the sieve passage side of the light diffusing agent obtained by measuring with a laser set flowmeter (microphone α track FRA) [; am]

A preferred embodiment is a thermoplastic resin composition in which the total amount of the extinguishing thermoplastic resin additive and the light diffusing agent is 0.5 to 5 parts per 100 parts by weight of the thermoplastic resin. ).

In a preferred embodiment, the thermoplastic composition has a weight ratio of the light diffusing agent to the thermoplastic resin additive for erasing of from 0 to〗 to 10 (claim 10).

BRIEF DESCRIPTION OF THE FIGURES

Figure 1 is an electron micrograph (× 500) of a conventional light diffusing agent, synthetic calcium carbonate.

FIG. 2 is an electron micrograph (× 500) of heavy calcium carbonate which is a thermoplastic resin additive for matting according to the present invention.

FIG. 3 shows a typical particle size distribution of heavy calcium carbonate, which is a thermoplastic resin additive for erasing of the present invention.

Fig. 4 shows a typical distribution of abundance of general heavy calcium carbonate. BEST MODE FOR CARRYING OUT THE INVENTION

A feature of the erasing thermoplastic resin additive of the present invention resides in the use of heavy calcium carbonate whose particle size and particle size distribution are strictly controlled.

Heavy calcium carbonate has a more specific polyhedral structure (S) as shown in Fig. 2 compared to a synthetic carbonated runum having a substantially hexahedral structure as shown in Fig. 1, which is conventionally used as a light diffusing agent. Or more). The thermoplastic resin additive for quenching, consisting of heavy carbon dioxide rubium of the invention, Although the reason for effectively providing the resin with deleterious properties is unknown, it is presumed to be due to having this unspecified polyhedron and controlling the particle size and particle size distribution to specific ranges.

In addition, the thermoplastic resin additive for matting of the present invention is made of heavy calcium carbonate as a raw material, so that it is inexpensive in terms of cost, and is blended because of its excellent particle dispersibility-fluidity and jet flowability. Workability at the time is good. Heavy calcium carbonate constituting the thermoplastic resin additive for erasing of the present invention has a 50% diameter A on the sieve passing side of 2 A ≤ 30, preferably 4 ≤ A ≤ 20, and more preferably 8 ≤ A ≤I 6 must be satisfied.

If the 50% diameter A exceeds 30 / m on the passing side on the sieve, not only does the delusterability decrease, but also the physical properties such as impact resistance and elongation of the resin decrease, further affecting the surface smoothness. Is not preferred. When A is not imprinted in 2 im, the opacity increases due to the light scattering of the calcium carbonate itself, and the total light transmittance decreases, so that it becomes difficult to obtain a desired total light transmittance, which is not preferable. No.

The weight cumulative percentage B of the particle diameter 1/2 of the 50% diameter A on the sieve passing side is 0≤B≤25, preferably 0≤B≤20, more preferably 0≤B≤15. As B approaches 0, the presence of fine particles decreases, and the desired glossiness can be imparted without adverse effects such as total light transmittance and impact resistance on the resin. On the other hand, if B exceeds 25, the amount of fine particles in the additive increases, and the fine particles decrease the total light transmittance, which is not preferable.

The value C obtained by dividing the cumulative 90% diameter on the sieve passing side by the 10% diameter is 1 ≤ C ≤ 25, preferably 1 ≤ C ≤ 20 and more preferably 1 ≤ C15. As the C value approaches 1, the particle size distribution becomes sharper, and it becomes possible to impart a desired attractiveness to the resin without adverse effects such as total light transmittance and impact resistance. On the other hand, when the C value exceeds 25, the particle size distribution becomes broad, and fine particles and coarse particles Fine particles reduce the total light transmittance due to the presence of particles, and coarse particles reduce the physical properties such as impact resistance of the resin, which is not preferable.

Similarly, the value D obtained by dividing the sieve passing side cumulative 75% by the 25% diameter is 1 ≤ D3, preferably 1 ≤ D ≤ 2.5, and more preferably 1 ≤ D2. As D approaches 1, the particle size distribution becomes sharper, and it becomes possible to impart a desired glossiness to the resin without giving adverse effects such as total light transmittance and impact resistance. On the other hand, if D exceeds 3, the particle size distribution becomes wider and fine particles and coarse particles are mixed, so that the fine particles reduce the total light transmittance and the coarse particles lower the physical properties such as impact resistance of the resin. Therefore, it is not preferable.

(4) The size of the kid is adjusted to 100 m or less, preferably 90 / zm or less, and more preferably 60 m or less. If the maximum particle diameter E force exceeds 00 // m, it will not only adversely affect the impact resistance etc. of the resin itself, but also a plate with a thickness of 1 to 3 mm · Sheet 100 / Π! Protrusions are likely to be formed on the surface of a film having a thickness of about 1 mm, which is not preferable because the product may be damaged.

In addition, when the dispersion of the additive in the resin is not sufficient, the fine particles adhere to the coarse particles, and a predetermined number of particles cannot be compounded in the resin, and a desired glossiness may not be obtained. .

For reference, FIG. 3 and FIG. 4 show typical particle size distributions of heavy carbonic acid lump, which is the thermoplastic resin additive for erasing of the present invention, and heavy calcium carbonate, which is generally used.

Generally, the classified heavy calcium carbonate has a particle size content having two peaks (FIG. 4), whereas the heavy calcium carbonate of the present invention is apparently obtained by intentionally removing fine particles. Yes (Figure 3).

斃消and Yonetsu thermoplastic resin additive of the present invention, constant pressure gas type specific surface area Sw is preferably 2000~l5000 cmVg, and more preferably from 3,000 to 7,500 cm ² / g, more preferably at 4000-6000 cm ² / g is there. When S w exceeds 15000 cm V g, increasingly fine particles present in the additive, fine particles are not preferable to Tei减the total light permeability, also, but if less than 2000 cm ² / g, the resin itself resistant Not only adversely affects the impact, etc., but also the anti-glare effect is drastically reduced, and furthermore, projections are easily formed on the surface of a plate having a thickness of about 1 to 3 mm and a thickness of about 100 m to 1 mm. The product may be damaged, which is not preferable.

To improve the fluidity and dispersibility of baby calcium carbonate in resin, and to prevent aggregation of heavy carbonated calcium carbonate, a hydrophobicity-imparting agent is used in an amount of 0.01 to 5 wt. More preferably, it is added to 0.1 to 4% by weight of heavy calcium carbonate and subjected to a surface treatment, whereby a better thermoplastic resin composition can be obtained.では If the amount of the water-imparting agent is less than 0.01% by weight, the above-mentioned surface treatment effect cannot be sufficiently exerted. On the other hand, if the amount exceeds 5% by weight, the surface treatment agent becomes excessively large due to an excessive amount of the surface treatment agent. It is not preferable because the predation phenomenon that the treatment agent oozes may be caused.

The hydrophobicity-imparting agent used in the present invention is not particularly limited as long as it imparts hydrophobicity to heavy calcium carbonate. Specific examples thereof include oleic acid, lauric acid, myristic acid, and myristic acid. Fatty acids such as isotridecyl, palmitic acid, behenic acid, stearic acid, isostearic acid, salts and derivatives thereof, and the above-mentioned salts include Na, K, and Li alkali metal salts or ammonium salts; and Metallurgical lubricants, such as barium stearate, potassium stearate, calcium stearate, aluminum stearate, zinc stearate, magnesium stearate or a complex thereof. Esters include higher fatty acid esters of monohydric alcohols and higher fatty acids of polyhydric alcohols. Fatty acid ester-based lubricants such as acid esters, monox-type long-chain esters or partial hydrolysates thereof; stearyl alcohol, etc. Higher alcohols or branched higher alcohols; C _ie more flow paraffin, micro Chris evening Nwakkusu, natural paraffin, synthetic paraffin, Poriorefui Nwakkusu and their partial oxide or fluoride, aliphatic hydrocarbons such as chloride Lubricants: Silicone oil, soybean oil, coconut oil, bamboo kernel oil, syrup oil, nayu oil, cottonseed oil, drill oil, castor oil, tallow, squalane, lanolin, hydrogenated oil, etc. Carboxylates such as N-acyl amino acid salts, alkyl ether carboxylates, and azylated peptides; alkyl sulfonates, alkylbenzenes and alkylnaphthalene sulfonates, sulfonatesuccinates, and Ichiseki refine sulfonates Sulfonates such as N, N-acyl sulfonate; sulfated oils, alkyl sulfates, Sulfates such as kill ether sulfates, alkylaryl ether sulfates and alkylamide sulfates: Phosphate salts such as alkyl phosphates, alkyl ether phosphates and alkylaryl ether phosphates; aliphatics Cationic surfactants such as ammonium salt, aliphatic 4-ammonium salt, benzalkonium salt, benzethonium chloride, pyridinium salt, imidazolinium salt, etc .; Amphoteric surfactants; polyoxyethylene alkyl ether, polyoxyethylene secondary alcohol ether, polyoxyethylene alkyl phenyl ether, polyoxyethylene sterol ether, polyoxyethylene lanolin derivative, alkylphenol formalin Compounds, etc., ethylene oxide derivatives, polyoxyethylene propylene propylene block polymer, polyoxyethylene polyoxypropylene alkyl ether, borooxyethylene dalyserin fatty acid ester, boroethylene castor oil and hardened Castor oil, polyoxyethylene sorbitan fatty acid ester, boroxyethylene sorbitol fatty acid ester, polyethylene glycol fatty acid ester, fatty acid monoglyceride Non-ionics such as lid, polyglycerin fatty acid ester, polyglycerin fatty acid ester, sorbin fatty acid ester, fatty acid alcohol amide, boroxyethylene fatty acid ester amide, polyoxyethylene alkylamine, alkylamine oxide, etc. Surfactants; Fluorosurfactants; Reactive surfactants such as polyoxetylenearylglycidylnonylphenyl ether, silane coupling agents, titanate coupling agents, etc .; Hydroxyl cellulose, carboxymethyl cellulose, etc. And the like. These can be used alone or in combination of two or more. Among these, fatty acids and fatty acid esters are preferable because they are inexpensive and have a high dispersing effect. The surface treatment method is not particularly limited, and may be any of a wet method and a dry method.

Furthermore, by adding and mixing a fluidity aid to the hydrophobicity-imparting agent, the fluidity of the heavy calcium carbonate itself and the dispersibility of the heavy carbon dioxide in the thermoplastic resin are improved.

The flow aid has a fine particle powder having an average particle diameter of 1/10 or less of the average particle diameter of the heavy calcium carbonate of the present invention having a surface roughness of 10 to 800111 ³ /. preferable.

Specific examples of the flow aid used in the present invention include talc, silicic anhydride, bentonite, kaolin, magnesium oxide, magnesium carbonate, magnesium silicate, zinc oxide, magnesium hydroxide, colloidal silica, diatomaceous earth. And fine powders such as magnesium stearate, fumed silica, fused silica, silica, constarch, starch, calcium silicate and the like. These may be used alone or in combination of two or more. Among them, silicic anhydride, colloidal silica, fumed silica, and fused silica are preferred in that the fluidity improving effect of the heavy calcium carbonate of the present invention is high. The amount of the flow aid added is 0.01 to 5% by weight based on the weight of the heavy carbon dioxide The range is preferred, with 0.1 to 4 weight being more preferred. If it is less than 0.01% by weight, the effect of improving the fluidity is insufficient, and if it exceeds 5% by weight, the effect of imparting fluidity can be obtained. When blended, the total light transmittance of the thermoplastic resin tends to decrease, which is not preferable. The fluidity aid is added to the above-mentioned hydrophobicity imparting agent and surface-treated to heavy calcium carbonate.

The erasable thermoplastic resin additive of the present invention is added to thermoplastic resins such as (meth) acrylic resin, styrene resin, polycarbonate resin, polyester resin, vinyl chloride resin, and ABS resin to perform various molding processes. It is used for coverings for lighting fixtures, lighting signs, various displays, loosing, signs, etc.

添加 The addition amount of the erasing thermoplastic resin additive cannot be specified unconditionally depending on the type of the thermoplastic resin, the desired total light transmittance, anti-glare property, glossiness, etc., but is generally 0 per 100 parts by weight of the thermoplastic resin. A range of 5 to 5 parts by weight is appropriate. When the amount of the thermoplastic resin additive for anti-glare is less than 0.5 part by weight, the effect of adding the additive such as anti-glare property and anti-glare property is not sufficiently exhibited. On the other hand, when the amount exceeds 5 parts by weight, the resin composition is used. The total light transmittance, impact resistance, elongation, strength, workability, etc. of the steel are reduced. When the thermoplastic resin additive for erasure of the present invention is added to the above resin, it is used alone or in combination with another light diffusing agent according to the purpose of use.

The fibrous-erasing thermoplastic resin additive of the present invention has an effect as a light-diffusing agent in addition to imparting an anti-glare property. Although transparency and anti-glare properties are also given at the same time, there are cases where it is not always possible to sufficiently cope with the recent needs of various tastes. In such a case, it is desirable to use together with a light diffusing agent, whereby the total light transmittance / the antiglare property and the gloss can be adjusted. Light diffusion agents include calcium carbonate, antimony trioxide, antimony pentoxide, barium sulfate, basic magnesium carbonate, titanium oxide, zinc oxide, aluminum oxide, aluminum hydroxide, magnesium hydroxide, zinc borate, and quartz. Crystalline Silica 'Amorphous Silica · Glass Bead' Lithium Fluoride · Calcium Fluoride · Talc 'My Strength' Zeolite 'Hydrotalite-Wallastonite-Tobernite-Gyrolite-Zonolite. Tobermorite-Dawsonite 'Apa Palgitto' Inorganic powders of power resin, (meth) acrylic resin, transparent plastics such as styrene resin, polycarbonate resin and vinyl chloride resin, and organic materials such as cross-linked polymerized polymer These are used alone or in combination of two or more.

In addition, it is preferable to appropriately apply the surface treatment agent and the flow aid applied to the heavy calcium carbonate to the above light diffusing agent according to the use and purpose. The light diffusing agents mentioned above may be those which are commonly used, but their cumulative 50% diameter F on the sieve passing side is 0.5≤F≤20, preferably l F≤iO, more preferably 3≤F 7 are preferably used in order to more effectively exhibit the extinction property, total light transmittance, and antiglare property of the thermoplastic resin composition of the present invention. In particular, synthetic calcium carbonate, barium sulfate, and glass beads satisfying the above-mentioned conditions. A light diffusing agent consisting of a sily force is preferably used. Among them, synthetic calcium carbonate has a desired total light transmittance and antiglare property due to its hexahedral shape. Is most preferable in that it is easy to express and set.

The ratio of the light diffusing agent to the additive of the thermoplastic resin for saturation is preferably in the range of 0.1 to 10 in terms of weight ratio of the former to the latter. If it is less than 0.1, the effect of adding the light diffusing agent is insufficient, and if it exceeds 10, the anti-glare property increases, but the total light transmittance decreases, and the energy of the light source is reduced to obtain a desired brightness. It is not preferable because it needs to be raised. Hereinafter, the (meth) acrylic resin composition will be described in more detail by way of example.

The (meth) acrylic resin used in the present invention may be a usual (meth) acrylic resin, for example, a homopolymer of methyl methacrylate or 50% by weight or more of methyl methacrylate and other polymers. Any of a copolymer with a vinyl monomer may be used.

Examples of the above-mentioned vinyl monomers include ethyl methacrylate, butyl methacrylate, hexyl methacrylate, phenyl methacrylate, benzyl methacrylate, 2-ethyl methacrylate, and 2-methacrylic acid. Methacrylic acid esters such as hydroxyethyl, methyl acrylate, ethyl acrylate, butyl acrylate, acrylic acid π-hexyl, phenyl acrylate, benzyl acrylate, 2-ethyl acrylate, and acrylic acid 2-acrylic acid esters such as hydroxylethyl, unsaturated acids such as methacrylic acid and acrylic acid, styrene, monomethylstyrene, acrylonitrile, methacrylonitrile, maleic anhydride, phenylmaleimide, and cyclohexylmaleide These can be used alone or Are used in combination of two or more.

The copolymer may contain a glutaric anhydride unit and a glutarimide unit, and may be a homopolymer, a copolymer obtained by blending a gen-based rubber, an acryl-based rubber, or the like with the copolymer.

The (meth) acrylic resin composition of the present invention is obtained by adding the (meth) acrylic resin to the above-mentioned thermoplastic resin additive for saturating the present invention or the thermoplastic resin additive for matting the present invention and the above-mentioned light. It is obtained by adding a diffusing agent.

The amount of the dulling thermoplastic resin additive of the present invention to be added to the above (meth) acrylic resin is appropriately selected depending on the glossiness, total light transmittance and antiglare property of the target resin composition. Powerful, 0.1% for 100 parts by weight of (meth) acrylic resin It is desirable to use 5 to 5 parts by weight, preferably 1 to 4 parts by weight, more preferably 1.5 to 3 parts by weight. If the addition amount of the thermoplastic resin additive for anti-glare exceeds 5 parts by weight, the resulting resin composition has reduced total light transmittance-impact resistance and elongation, and becomes bright when used for lighting covers and the like. Not only is the pod strength insufficient, but the transmitted light is colored and the desired physical properties cannot be obtained. On the other hand, when the addition amount is less than 0.5 part by weight, it is not preferable because the resulting resin composition cannot be provided with sufficient anti-glare property and the object of the present invention cannot be achieved.

The amount of the light diffusing agent to be added to the above (meth) acrylic resin in combination with the thermoplastic resin additive for matting of the present invention is determined by the gloss of the target resin composition, the total light transmittance, and the antiglare property. The total amount of the thermoplastic resin additive for matting of the present invention and the light diffusing agent is preferably 0.5 to 5 parts by weight with respect to 100 parts by weight of the (meth) acrylic resin. Preferably, it is in the range of 1 to 4 parts by weight, more preferably 1.5 to 3 parts by weight.

If the total amount exceeds 5 parts by weight, the resulting resin has a total light transmittance-impact resistance.The elongation is reduced, and when used for lighting covers, etc., not only lack of brightness and strength but also transmission. It is not preferable because the light is colored and the desired physical properties cannot be obtained. On the other hand, if the total amount is less than 0.5 part by weight, the resulting resin composition cannot be provided with sufficient anti-glare property and anti-glare property, and the object of the present invention is not achieved.

Mixing of the (meth) acrylic resin and the light-diffusing agent to be added together with the matting thermoplastic resin additive of the present invention, or the matte ripening thermoplastic resin additive of the present invention. Although there is no particular limitation without any problem, for example, a Henschel mixer ■ After mixing and stirring with a mixer such as a tumbler, the mixture is pelletized with a usual extruder to obtain the acrylic resin composition for erasure (medium) of the present invention. In the above method, when the anti-glare thermoplastic resin additive of the present invention is used in combination with a light diffusing agent, the anti-glare thermoplastic resin additive and the light diffusing agent are added to the resin at the same time. The pelletizing may be performed separately, or the pellets may be separately added to the resin, pelletized, and then both pellets may be melt-kneaded again and pelletized by an extruder.

A thermoplastic resin composition composed of polystyrene resin, polycarbonate resin and polyester resin can also be obtained by the same method as the above (meth) acrylic resin.

照明 A method for manufacturing a lighting cover or the like provided with an erasable property is a method in which the resin composition of the present invention is subjected to sheet processing using an extruder equipped with a vent so that the surface of the sheet is smooth. Depending on the desired application and physical properties, 1) Laminating the resin composition sheet of the present invention on a sheet of an acryl resin, a polycarbonate resin, a vinyl chloride resin, etc. The desired illumination cover may be obtained, and if necessary, the surface of the obtained resin plate may be processed into a sheet in a mat shape. The thermoplastic resin composition of the present invention generally comprises It may contain other additives, such as pigments, dyes such as fluorescent whitening agents and bluing agents, various stabilizers, antioxidants, processing aids, and various additives such as antistatic agents. According to the present invention, by using the thermoplastic resin additive for erasing of the present invention, the additive does not agglomerate in the thermoplastic resin composition, and the coarse and agglomerated particles as well as the fine particles Since it does not contain particles, it has extremely excellent light transmission without impairing impact resistance, elongation, surface smoothness, and appearance of lighting covers and the like obtained by molding and processing the thermoplastic resin. · It has anti-glare properties and can be given an eradicating property.

Hereinafter, the present invention will be described more specifically with reference to examples. It is needless to say that the PC screen is not limited to these embodiments.

In addition, the measuring method of each characteristic value is shown below.

Gulla degree distribution>

After suspending 5 g of heavy calcium carbonate or a light diffusing agent in 50 cc of methanol, the suspension is dispersed for 60 seconds with an ultrasonic dispersing machine (US-300T, manufactured by Nippon Seiki Seisaku-sho, Ltd.), and the methanol suspension is measured with a laser particle size distribution analyzer. The measurement was performed using a machine (manufactured by Nikkiso: Microtrack FRA).

Specific surface area of powder

The measurement was performed using a constant pressure aeration type powder specific surface area measurement equipment (manufactured by Shimadzu Corporation).

Total light transmittance>

According to ASTM D-1000-6-1, the measurement was performed with an integrating sphere HTR method.

Light diffusivity>

The value obtained by dividing the average of the light intensity transmitted at angles of 20 ° and 70 ° measured by Goniohotome Ichiichi (HR-100, manufactured by Murakami Color Research Laboratory) by the light intensity transmitted at an angle of 5 ° was used. It was determined as a percentage. This light diffusivity was used as an index of antiglare properties.

The light-diffusing plastic was visually observed, and evaluated in five steps according to the following evaluation criteria.

5 points: The surface is smooth with no visible irregularities.

4 points: Fine irregularities are slightly visible on a part of the surface, but there is no practical problem.

3 points: Fine irregularities are observed on the entire surface, but there is no practical problem. 2 points: Fine irregularities are observed on the entire surface, and coarse irregularities are partially observed. There is a practical problem.

1 point: Coarse irregularities are observed on the entire surface, which is very problematic in practical use. Surface gloss>

A 60-degree mirror surface was measured using a gloss meter GM-26D manufactured by Murakami Color Research Laboratory, which was used as an index of glossiness.

The obtained resin plate was measured according to ASTM D256.

A five-point scale was evaluated according to the following evaluation criteria.

A: Anti-glare property · Total light transmittance · Anti-glare property, resin strength · Very smooth resin plate, ideal for use as an anti-glare lighting cover.

B: §S extinction · Total light transmittance << Anti-glare · Resin strength · Smoothness of resin plate is good, suitable for lighting cover with extinction.

C: Anti-glare property · Total light transmittance · Anti-glare property · Resin strength · The resin plate has relatively good smoothness and can be used as a matte lighting cover.

D: Erasable, all light transmissive, anti-glare, resin strength, and smoothness of resin plate are poor, and there is a practical problem in using as an eraser lighting cover.

E: Difficulty · Total light transmittance · Anti-glare · Resin strength · Smoothness of resin plate is poor, making it impractical to use as a matte lighting cover.

Examples 1 to 6

The white sugar-lime limestone is crushed and classified, and the cumulative percentage of sieve passing side B and the cumulative percentage of passing side B with 50% diameter of the sieve passing side shown in Table 1 are 50% A and 50% of the 50% diameter of the sieve passing side shown in Table 1. 90% diameter divided by 10% diameter C, 25% Amorphous polyhedral heavy carbonated calcium powder having a value D divided by the diameter, a maximum diameter L, and a constant pressure aeration type powder specific surface area was prepared, and a thermoplastic resin additive for deactivating was obtained. .

Observation of the obtained powder by SEM photograph revealed that the powder was a hexahedron or more.

Example? ~ Ten

To the heavy carbonated calcium carbonate of Example 6, a hydrophobicity imparting agent was added in an amount of X parts by weight based on 100 parts by weight of the heavy calcium carbonate powder, and the mixture was heated and mixed with a Henschel i-mixer to erase thermoplasticity. A resin additive was obtained.

Examples 11 to 14

The fluidity aid β was added to the heavy carbonated calcium carbonate of Example 10 in an amount of 100 parts by weight of heavy carbonated calcium, and the mixture was heated and mixed with a Hensile mixer. An additive was obtained.

Example 15

To the heavy calcium carbonate of Example 4, 3.9 parts by weight of stearic acid was added as a hydrophobicity imparting agent α to 100 parts by weight of heavy calcium carbonate, and the flow aid was used as a fluidizing aid to adjust the abductor diameter. However, 2 parts by weight of 0.005 to 0.05 m of fumed silica power was added to 100 parts by weight of heavy carbon dioxide rubber, and heated and mixed with a Henschel mixer to obtain a thermoplastic resin additive for erasing.

A B c D

ro

50% diameter cumulative sifter passing through sieve [/ rn]

Fifjg product 50% of the particle size of 50% diameter 錢 passing cumulative percentage [¾] sieve passing «side cumulative« 30% diameter divided by 10% diameter glare

Sieve passing 劂 IS obtained by dividing the cumulative 75% g by 25% diameter

Maximum particle diameter (Um)

Constant-pressure ventilation type specific surface area CcmZ / g]

Hydrophobicity imparting agent

A Addition of hydrophobicity-imparting 劓 to heavy H-carbohydrate calcium (heavy s part) Flowability aid

Amount of flow aid added to heavy calcium carbonate (parts by weight)

Comparative Examples 1 to 5

Pulverize and classify the white saccharified limestone and accumulate 50% of the sieve passing side A shown in Table 2; The value obtained by dividing the cumulative 90% diameter on the passing side by 10% diameter (: The value obtained by dividing the cumulative 75% diameter on the sieve passing side by 25% diameter D, the maximum diameter of the abdomen E, and the constant pressure aerated powder specific surface area Sw An amorphous polyhedral heavy calcium carbonate powder was prepared to obtain an extinguishing thermoplastic resin additive.

Observation of the obtained powder by SEM photograph S revealed that it was a polyhedron (6 or more).

Comparative Example 6

A synthetic calcium carbonate shown in Example 4 of JP-A-10-130020 was prepared and used as a thermoplastic resin additive for erasing. A, B, C, D, and E of the synthetic calcium carbonate were as shown in Table 2.

Comparative Example 7

Commercially available fused silica was separated and used as a thermoplastic resin additive by applying a fused silica force that satisfies the conditions of A, B, C, D, and E in Table 2.

Table 2

A ϋPassing side cumulative 孭 50 ¾ diameter (m)

B Cumulative percentage of sieve passing side of 1/2 of 50% diameter of sieve passing side [¾] C 90% diameter of sieve passing side divided by 10% diameter

D Value obtained by dividing the 75% diameter by the 25% diameter

E bun large particles ¾O m)

Sw Constant E-vented powder specific surface area! : cm ² / g)

a Hydrophobicity imparting agent

X Heavy 珐 Addition of water-based agent to calcium (Heavy * part) β Flow aid

流動 Addition of flow aid to heavy S calcium carbonate fi (heavy: 1 part) Examples 16 to 23, Comparative Examples 8 to 11

M'parts by weight of a thermoplastic resin additive M for gloss reduction is added to 100 parts by weight of a partial copolymer of methyl methyl acrylate (copolymerization ratio of styrene: 18% by Sumitomo Chemical Co., Ltd .: Sumivex-EXA) The mixture was stirred at high speed for 60 seconds with Henschel Mixer to sufficiently disperse the mixture. After that, the resin temperature was set to 250 using an extruder with an S5 mm ø vent and a coat hanger die with a die width of SOOmm. (: Extruded into a sheet shape and processed into a plate shape by three rolls of polishing, to obtain a sample plate having a thickness of 2 mm.

Table 3 shows the characteristic values related to the optical characteristics of the obtained sample plate and the overall evaluation.

Table 3

i

M Example number of thermoplastic resin additive for matte M ': Compounding amount of thermoplastic resin additive for matte [weight gfl

Example 24.25

Methyl methacrylate partial copolymer (copolymerization ratio of styrene 18%, manufactured by Sumitomo Chemical Co., Ltd .: Sumbexu EXA 00 parts by weight, thermoplastic resin additive for erasing 18 M.N (light diffusing agent) M 'and N' parts by weight were blended, and mixed and stirred at high speed for 60 seconds with a Henning mixer to sufficiently disperse the resin.After that, the resin temperature was increased using an extruder with a 65 mm vent and a coat hanger die with a die width of 600 mm. It was extruded into a sheet at 250 ° C and processed into a plate shape by a three-hole boring machine to obtain a 2 mm thick sample plate.

Table 4 shows the characteristic values related to the optical characteristics and the overall evaluation of the obtained sample plate.

Four

Example number of fft eraser thermoplastic resin additive 滟 Compounding amount of eraser thermoplastic resin additive [overlapping part] Comparative example number of light diffusing agent

Formulation of light diffusing agent i [parts]

Examples 26 to 33, Comparative examples 12 to 15

To 100 parts by weight of a polyester resin (manufactured by Dai-Bon Ink Chemical Industry Co., Ltd .: CR3500), add the thermoplastic resin additive for gloss removal of Examples 1, 6, 15 and Comparative Examples 1, 2, 6, and 7 to 2 parts by weight. Parts by weight were mixed and uniformly dispersed with a tumbler. In the same manner as in Example 8, a sample plate having a thickness of 2 mm was obtained. Table 5 shows the characteristic values related to the optical characteristics and the overall evaluation of the obtained samples.

Table 5

M: 16 Example number of plasticizer additive for eraser ': | Compounding amount of thermoplastic resin additive for eraser [parts by weight]

Examples 34, 35

Partial copolymer of methyl methacrylate (copolymerization ratio of styrene: 18% by weight, Sumitomo Chemical Co., Ltd .: Sumivex EXA) 100 parts by weight of thermoplastic resin additive M, N (light diffusing agent) Μ 'and Ν' parts by weight were mixed with each other, and mixed and stirred sufficiently at a high speed for 60 seconds with a Henschel mixer to sufficiently disperse.A sample plate having a thickness of 2 mm was obtained in the same manner as in Example 8. .

Table 6 shows the characteristic values related to the optical characteristics and the overall evaluation of the obtained sample plate.

¾6

M: Example number of 8S thermoplastic resin additive for erasing ': 配合 Compounding amount of thermoplastic resin additive for erasing [overlapping part]

N: Comparative example number of light diffusing agent

N ': Compounding light diffusing agent i [Heavy 4 parts]

Examples 36 to 43, Comparative examples 16 to 19

100 parts by weight of a polycarbonate resin (Mitsubishi Chemical Corporation: NOVAREX 7030) was blended with M 'parts by weight of a thermoplastic resin additive M for fascinating, and the mixture was evenly dispersed with a Kumblar. In the same manner as in Example 8, a sample plate having a thickness of 2 mm was obtained. The following table shows the characteristic values related to the optical characteristics and the Suigo evaluation of the obtained samples.

Example 36 Example 37 Example 38 Example 39 Example 40 Example ^ 141 Example 42 laugh Ratio example 16 Comparative example 19

M Example 15 English puncture 15 Example 15 Example 15 Example 15 Example 15 Example 1 Example 6 Comparative example 1 Comparative example 2 Comparative example 6 Comparative example 7

Μ '0.6 4.8 1.1 3.a 1.6 2.a 4.8 0.6 1.6 2 β 2.B 1.6 Total light transmittance 74 50 69 54 64 5a 45 80 43 73 64 66 Light diffusivity 44 71 51 66 57 61 77 37 82 32 71 42 Smoothness 5 3 5 3 5 4 3 4 3 1 5 5 Gloss 20 12 18 13 16 14 20 19 27 25 41 40 Izod strength 3.9 2.5 3.7 2.9 3.5 3.2 2.4 2.3 3.4 3.5 3.7 α.6 Overall evaluation CCBBAACCDDE Ε

: Example number of thermoplastic resin additive for erasing

Μ ': Compounding amount of K-erasing thermoplastic resin additive [part by mass]

Examples 44, 45

Polycarbonate resin (Mitsubishi Chemical Corporation: NOVAREX 7030) 100 parts by weight of M 部 and N 'parts by weight of the thermoplastic resin additives M and N are blended and dispersed uniformly in a tumbler. Was.

In the same manner as in Example 8, a sample plate having a thickness of 2 mm was obtained. Table 8 shows the characteristic values related to the optical characteristics and the overall evaluation of the obtained sample plate.

Table 8

M Example number of thermoplastic resin additive for eraser M '配合 Compounding amount of thermoplastic resin additive for eraser [overlapping part]

N Comparative example number of light diffusing agent

Compounding amount of N 'light diffusing agent [Heavy i part]

Industrial applicability

As described above, the thermoplastic resin additive for matte of the present invention is blended with a thermoplastic resin to provide a thermoplastic resin composition excellent in matteness, antiglare properties and total light transmittance. It is useful for lighting covers, lighting signs, various displays, groosing, signs, etc.

Claims

The scope of the claims

1. A matte thermoplastic resin additive characterized by being composed of heavy calcium carbonate satisfying the particle size distribution constitution of the following formulas (1) to (5).

2≤A≤3 0 (1)

0≤B≤ 2 5 (2)

1 ≤ C≤ 2 5 (3)

1 ≤D≤ 3 (4)

E≤ 1 0 0 (5)

However,

A: Laser flow rate 7fi meter (Microtrac FRA> Measured 50% diameter of heavy calcium carbonate accumulated on the sieve passing side [m]

B: Cumulative passing side of heavy calcium carbonate obtained by measuring with a laser set flow meter (Microtrac FRA) 50% ]

C: The value obtained by dividing the 90% diameter by the 10% diameter on the sieve passing side of heavy calcium carbonate obtained by using a laser type flowmeter (Microtrac FRA) [1]

D: The value obtained by dividing the cumulative 75% of the heavy calcium carbonate passing through the sieve obtained by measuring with a laser flowmeter (Microtrack FRA) by the 25% diameter [-]

E: Maximum particle size [^ m] of heavy calcium carbonate obtained by measuring with a flow meter (Microtrac FRA).

2. The matte ripening plastic resin additive according to claim 1, wherein a constant pressure aeration type powder specific surface area S w of the heavy carbon dioxide ruthenium is from 2000 to 15000 cm ² / g.

3. The matte according to claim 1 or 2, wherein the heavy calcium carbonate is surface-treated with 0.01 to 5 parts by weight of a hydrophobicity-imparting agent based on 100 parts by weight of heavy calcium carbonate. Thermoplastic resin additive.

4. The thermoplastic resin additive for matting according to claim 3, wherein 0.01 to 5 parts by weight of a flow aid is added to 100 parts by weight of heavy calcium carbonate to the hydrophobicity imparting agent.

5. A thermoplastic resin composition comprising the mature thermoplastic resin and the thermoplastic resin additive for extinction according to any one of claims 1 to 4 blended therein.

6. The thermoplastic resin composition according to claim 5, wherein the blending amount of the thermoplastic resin additive for antiglare is 0.5 to 5 parts by weight based on 100 parts by weight of the thermoplastic resin.

7. A thermoplastic resin composition, characterized in that the thermoplastic resin additive and the light diffusing agent according to any one of claims 1 to 4 are blended with the thermoplastic resin.

8. The thermoplastic resin composition according to claim 7, wherein the light diffusing agent is at least one selected from synthetic calcium carbonate-barium sulfate / glass beads / silicone force satisfying the following formula (6).

0.05≤ F≤10.0 (6)

However,

F: Cumulative 50% diameter on the sieve passing side of the light diffusing agent obtained by measurement with a laser flowmeter (Microtrac FRA) [m]

9. The thermoplastic resin composition according to claim 7 or S, wherein the total amount of the extinguishing thermoplastic resin additive and the light diffusing agent is 0.5 to 5 parts by weight based on 100 parts by weight of the thermoplastic resin.

1 0. The ratio of the light diffusing agent to the thermoplastic resin additive for starvation is 0.1 to 10 by weight. 10. The thermoplastic resin composition according to any one of items 9 to 9.