JP2008222863A - Masterbatch, method for producing the same, molded article produced by using the masterbatch and laminate produced by using the molded article - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a masterbatch having improved dispersibility of a hexaboride fine particle component in an acrylic resin molding material widely used as the roof material and wall material of buildings, window material, etc., of automobiles, etc., and to provide a method for producing the masterbatch, a molded article produced by using the masterbatch and a laminate. <P>SOLUTION: The masterbatch is produced by adding (C) an aggregation prevention agent to an alcohol dispersion of (A) hexaboride fine particles, evaporating the alcohol, and kneading the obtained powder with (D) an acrylic resin molding material in a molten state. The hexaboride fine particle (A) is surface-coated with a fluoroalkylsilane compound (B), and the aggregation prevention agent (C) is an acrylic polymer compound soluble in alcohols, compatible with the acrylic resin molding material (D) and free from functional group adsorbing to the surface of the hexaboride fine particle (A). <P>COPYRIGHT: (C)2008,JPO&INPIT

Description

  The present invention relates to a masterbatch and a manufacturing method thereof, a molded body using the masterbatch, and a laminate using the molded body, and more specifically, a roof material or wall material of a building, a window material of an automobile, etc. The present invention relates to a masterbatch in which the dispersibility of the hexaboride fine particle component is improved in an acrylic resin molding material widely applied to, and a production method thereof, and a molded body and a laminate using the masterbatch.

  In addition to visible light, ultraviolet rays and infrared rays are included in solar rays incident from so-called opening portions such as roof materials, wall materials, windows of automobiles, trains, airplanes, and doors of various buildings. Of the infrared rays contained in the sunlight, near infrared rays of 800 to 2500 nm are called heat rays, and cause the indoor temperature to rise by entering from the opening. In order to solve this problem, in recent years, in various building and vehicle window materials, arcades, ceiling domes, carports, etc. The demand for a heat ray shielding molded body that suppresses the temperature rise is rapidly increasing, and many patents relating to the heat ray shielding molded body have been proposed.

For example, a heat ray shielding plate in which a heat ray reflective film formed by vapor-depositing a metal or metal oxide on a transparent resin film is bonded to a transparent molded body such as glass, an acrylic plate, or a polycarbonate plate has been proposed (for example, Patent Document 1). 2 and 3). However, since the heat ray reflective film itself is very expensive and requires a complicated process such as an adhesion process, the heat ray shielding plate is expensive. Moreover, since the adhesiveness of a transparent molded object and a heat ray reflective film is not good, it has the fault that peeling of a film arises by a time-dependent change.
In addition, many heat ray shielding plates have been proposed in which a metal or metal oxide is directly deposited on the surface of the transparent molded body. However, when manufacturing this heat ray shielding plate, there is an apparatus that requires high vacuum and high-precision atmosphere control. Since it is necessary, it has a problem that mass productivity is poor and versatility is poor.

  In addition, for example, a heat ray shielding plate in which an organic near-infrared absorber typified by a phthalocyanine compound or an anthraquinone compound is incorporated into a thermoplastic transparent resin such as a polyethylene terephthalate resin, a polycarbonate resin, an acrylic resin, a polyethylene resin, or a polystyrene resin. And films have been proposed (see, for example, Patent Documents 4 and 5). However, in order to sufficiently shield the heat rays, a large amount of near-infrared absorber has to be blended, and when it is blended in a large amount, there is a problem that the visible light transmission ability is lowered. In addition, since organic compounds are used, application to buildings and vehicle window materials that are constantly exposed to direct sunlight has difficulty in weather resistance, and is not necessarily suitable.

  Further, for example, a heat ray shielding plate in which inorganic particles such as mica coated with titanium oxide or titanium oxide having heat ray reflectivity in a transparent resin such as acrylic resin and polycarbonate resin has been proposed (for example, In the heat ray shielding plate, it is necessary to add a large amount of heat ray reflective particles in order to increase the heat ray shielding ability, and the visible light transmission ability decreases as the blending amount of the heat ray reflective particles increases. It has the problem of end up. Further, when the addition amount of the heat ray reflective particles is decreased, the visible light transmission ability is increased, but the heat ray shielding ability is lowered, and it is difficult to satisfy both the heat ray shielding ability and the visible light transmission ability at the same time. In addition, when a large amount of heat ray reflective particles are blended, there is a problem from the strength aspect that the physical properties, particularly impact strength and toughness, of the transparent resin as a molded article are lowered.

Under such a technical background, the applicant of the present invention obtained a heat ray shielding coating solution containing hexaboride fine particles in various binders as a heat ray shielding component, and applied the coating solution to various molded bodies and then cured. A masterbatch obtained by melt-kneading and dispersing hexaboride fine particles in a heat-shielding film and a thermoplastic resin have been proposed (see, for example, Patent Documents 8 to 10 and 11).
Among the above, in the case of a masterbatch in which hexaboride fine particles are dispersed in a polycarbonate resin or a polyester resin, the hexaboride fine particles are usually contained in an acrylic dispersant having a functional group having an adsorption effect on the hexaboride fine particles. By melting and kneading the uniformly dispersed powder, polycarbonate resin, and polyester resin, a master batch that maintains uniform dispersibility without the formation of aggregates of hexaboride fine particles in the resin can be obtained. Therefore, the molded body using this was excellent in heat ray shielding ability and low in haze.
On the other hand, in the case of a masterbatch in which hexaboride fine particles are dispersed in an acrylic resin, the hexaboride fine particles are uniformly dispersed in an acrylic dispersant having a functional group having an adsorption effect on the boride fine particles, as described above. When melted and kneaded acrylic powder and acrylic resin are formed, aggregates of hexaboride fine particles are easily formed in the acrylic resin, resulting in insufficient dispersibility. The molded body using this master batch has excellent heat ray shielding ability. However, a unique problem different from the case of a masterbatch dispersed in a polycarbonate resin or a polyester resin has been found that haze (cloudiness) is increased and design properties are lowered.

For this reason, it is difficult to form an aggregate of hexaboride fine particles in the acrylic resin, and a masterbatch having sufficient dispersibility of the hexaboride fine particles has excellent heat ray shielding ability by using this, and haze There has been a demand for a molded article having low (cloudiness) and excellent design properties.
JP-A 61-277437 Japanese Patent Laid-Open No. 10-146919 Japanese Patent Laid-Open No. 2001-179887 JP-A-6-256541 JP-A-6-264050 JP-A-2-173060 JP-A-5-78544 JP-A-11-181336 JP 2000-96034 A JP 2000-169765 A JP 2004-59875 A

  An object of the present invention is to improve the dispersibility of hexaboride fine particle components in acrylic resin molding materials widely applied to roof materials and wall materials of buildings, window materials of automobiles, etc. in order to solve the above-mentioned problems. Another object of the present invention is to provide a master batch and a manufacturing method thereof, and a molded body and a laminate using the master batch.

  As a result of intensive studies aimed at solving the above-mentioned problems, the present inventors have added a fluoroalkylsilane compound to a slurry obtained by mixing micron-order hexaboride fine particles and alcohol, and pulverized them with a medium stirring mill. An alkylsilane compound-coated hexaboride fine particle dispersion is prepared, and has a functional group that is soluble in alcohol and compatible with an acrylic resin molding material and has an adsorption effect on the surface of the hexaboride fine particles. After adding and mixing the acrylic resin anti-agglomeration agent, the alcohol is volatilized from the resulting mixture, and the resulting powder is mixed with the acrylic resin molding material and melt-kneaded, so that in the acrylic resin molding material And found that a masterbatch with improved dispersibility can be obtained without forming aggregates of hexaboride fine particles, leading to the completion of the present invention. It was.

  That is, according to the first invention of the present invention, after the aggregation inhibitor (C) is added to the alcohol dispersion of the hexaboride fine particles (A), the alcohol is volatilized, and the obtained powder is acrylic. A method for producing a masterbatch by melt-kneading with a resin molding material (D), wherein the hexaboride fine particles (A) are surface-coated with a fluoroalkylsilane compound (B), while an aggregation inhibitor (C) is an acrylic polymer compound that is soluble in alcohol, has compatibility with the acrylic resin molding material (D), and does not have a functional group that adsorbs to the surface of the hexaboride fine particles (A). A method for producing a master batch is provided.

According to the second invention, in the first invention, the hexaboride fine particles (A) have the general formula XB ₆ (wherein the element X is La, Ce, Pr, Nd, Gd, Tb, Dy, A method for producing a masterbatch, characterized in that it is a hexaboride represented by Ho, Y, Sm, Eu, Er, Tm, Yb, Lu, Sr, or Ca. Provided.
According to the third invention, there is provided a method for producing a masterbatch, wherein, in the first invention, the average particle size of the hexaboride fine particles (A) is 500 nm or less.
According to the fourth invention, in the first invention, the hexaboride fine particles (A) disperse hexaboride particles having an average particle size of 1 μm or more in alcohol, and the fluoroalkylsilane compound (B ) Is added and then pulverized with a medium agitating mill to provide a method for producing a masterbatch.
According to the fifth invention, in any one of the first to fourth inventions, the content of the hexaboride fine particles (A) is 0.01 with respect to 100 parts by weight of the acrylic resin molding material (D). A method for producing a masterbatch, characterized in that it is ˜20 parts by weight, is provided.

According to a sixth invention, there is provided a method for producing a masterbatch, characterized in that, in the first invention, the fluoroalkylsilane compound (B) is represented by the following general formula (1).
YRSiX ₃ (1)
(In the formula, Y represents a fluorinated alkyl group having 1 to 12 carbon atoms, R represents an alkylene group having 2 to 4 carbon atoms, and X represents an alkoxy group having 1 to 4 carbon atoms.)

According to the seventh invention, in the first invention, the addition amount of the fluoroalkylsilane compound (B) is 0.01 to 5 parts by weight with respect to 1 part by weight of the hexaboride particles. A featured masterbatch manufacturing method is provided.
According to the eighth invention, in the first invention, the acrylic polymer compound of the aggregation inhibitor (C) is a (meth) acrylic acid hydroxyalkyl ester having 1 to 8 carbon atoms and 1 to 13 carbon atoms. There is provided a method for producing a masterbatch, which is a copolymer of (meth) acrylic acid alkyl ester.
Furthermore, according to the ninth invention, in the first invention, the addition amount of the aggregation inhibitor (C) is 1.0 to 50 parts by weight with respect to 1 part by weight of the hexaboride particles. A method for producing a masterbatch is provided.

On the other hand, according to the tenth invention, a powdery material obtained by the production method according to any one of the first to ninth inventions and containing hexaboride fine particles (A) and an anti-aggregation agent (C) is used as an acrylic resin. A master batch obtained by melt-kneading with the molding material (D) is provided.
According to an eleventh aspect, according to the tenth aspect, the master batch containing the acrylic resin molding material (D) is diluted and melted with the same or different acrylic resin as the acrylic resin molding material (D). A molded body that is kneaded and then molded into a predetermined shape is provided.
Furthermore, according to the twelfth invention, there is provided a laminate in which the molded article according to the eleventh invention is laminated on a thermoplastic resin molded article other than the acrylic resin molding material (D).

The master batch of the present invention is an acrylic polymer compound that is soluble in alcohol, compatible with an acrylic resin molding material, and does not have a functional group having an adsorption effect on the surface of hexaboride fine particles. Is obtained by melt-kneading a powdered product in which hexaboride fine particles coated with a fluoroalkylsilane compound are uniformly dispersed in an acrylic resin, so that the hexaboride fine particles in the acrylic resin are obtained. Unlike conventional master batches that were not sufficiently dispersed, the dispersibility was improved without the formation of aggregates of hexaboride fine particles in the acrylic resin.
For this reason, the molded object using the said masterbatch has the outstanding heat ray shielding ability, and its haze is also low and favorable. In addition, since the dispersibility is good as described above and the acrylic resin aggregation inhibitor is used, the weather resistance against rainwater received during use outdoors is also good. Therefore, excellent heat ray shielding ability for acrylic resin moldings widely used for building roofing materials, wall materials, window materials used in openings of automobiles, trains, airplanes, arcades, ceiling domes, carports, etc. And can be used in a wide range of fields.

  Hereinafter, the masterbatch of the present invention and the manufacturing method thereof, a molded body using the masterbatch, and a laminate using the molded body will be described in detail.

1. Manufacturing method of masterbatch The manufacturing method of the masterbatch of this invention is the powdery substance obtained by volatilizing alcohol after adding the aggregation inhibitor (C) to the alcohol dispersion of hexaboride fine particles (A). Is a method for producing a masterbatch by melt-kneading with an acrylic resin molding material (D), wherein the hexaboride fine particles (A) are surface-coated with a fluoroalkylsilane compound (B), while agglomerated. The inhibitor (C) is an acrylic polymer compound that is soluble in alcohol, compatible with the acrylic resin molding material (D), and does not have a functional group adsorbed on the surface of the hexaboride fine particles (A). It is characterized by being.

(A) Hexaboride Particles In the present invention, hexaboride fine particles are a component that exhibits a heat ray shielding effect, and are not limited as long as they have such a function.

Preferred hexaboride are those of the general formula expressed by the XB _6. Here, the element X is at least one selected from La, Ce, Pr, Nd, Gd, Tb, Dy, Ho, Y, Sm, Eu, Er, Tm, Yb, Lu, Sr and Ca. It is preferable. Specifically, lanthanum hexaboride LaB ₆ , cerium hexaboride CeB ₆ , praseodymium hexaboride PrB ₆ , neodymium hexaboride NdB ₆ , gadolinium hexaboride GdB ₆ , terbium hexaboride TbB ₆ , hexaboride Dysprosium DyB ₆ , holmium hexaboride HoB ₆ , yttrium hexaboride YB ₆ , samarium hexaboride SmB ₆ , europium hexaboride EuB ₆ , erbium hexaboride ErB ₆ , thulium hexaboride TmB ₆ , 6 boron Typical examples thereof include ytterbium iodide YbB ₆ , lutetium hexaboride LuB ₆ , lanthanum cerium hexaboride (La, Ce) B ₆ , strontium hexaboride SrB ₆ , calcium hexaboride CaB _{6, and the} like.

The hexaboride fine particles are preferably not oxidized on the surface, but are usually slightly oxidized, and to some extent avoid surface oxidation during the fine particle dispersion process. I can't. However, even in such a case, the effectiveness of developing the heat ray shielding effect is not changed, and therefore, hexaboride fine particles having an oxidized surface can be used.
The hexaboride fine particles have a higher heat ray shielding effect as the crystal completeness is higher, but even if the crystallinity is low and a broad diffraction peak is generated by X-ray diffraction, If the basic bond is composed of a bond between each metal and boron, it can be applied in the present invention in order to exhibit a heat ray shielding effect.

The hexaboride fine particles are colored powders such as gray black, brown black, and green black, and are dispersed in an acrylic resin molded material with a particle size sufficiently smaller than the visible light wavelength. Then, although visible light permeability is generated in the obtained heat ray shielding transparent resin molding, the infrared light shielding ability can be sufficiently maintained. The reason for this has not been elucidated in detail, but the amount of free electrons in these fine particles is large, and the absorption energy of indirect interband transition due to free electrons inside and on the surface of the fine particles is just in the vicinity of visible to near infrared. For this reason, it is considered that heat rays in this wavelength region are selectively reflected and absorbed.
Actually, in a film in which these fine particles are sufficiently finely and uniformly dispersed, the transmittance has a maximum value between wavelengths of 400 nm and 700 nm, and has a minimum value between wavelengths of 700 nm and 1800 nm. It has been observed that the difference between the maximum and minimum transmittance values is 15 points or more. Considering that the visible light wavelength is 380 nm to 780 nm and the visibility is a bell-shaped peak having a peak at around 550 nm, such a heat ray shielding transparent resin molding effectively transmits visible light, and other than that It has the characteristic of reflecting and absorbing heat rays effectively.

  Therefore, the average particle size of the hexaboride fine particles is 500 nm or less, preferably 300 nm or less. When the average particle diameter exceeds 500 nm, such a heat ray shielding transparent resin molded article containing hexaboride fine particles may not effectively transmit visible light, which is not preferable. However, if it is less than 30 nm, the dispersibility to an acrylic resin deteriorates and handling becomes difficult.

(B) Fluoroalkylsilane compound The above-described hexaboride fine particles need to be coated on the surface with the fluoroalkylsilane compound (B).

As a fluorosilane compound used for this invention, what is shown by General formula (1) is mentioned, for example.
YRSiX ₃ (1)
In the formula, Y represents a fluorinated alkyl group having 1 to 12 carbon atoms, R represents an alkylene group having 2 to 4 carbon atoms, and X represents an alkoxy group having 1 to 4 carbon atoms. Here, Y has a function of suppressing aggregation of the acrylic resin, and a fluorinated alkyl group having 2 to 10 carbon atoms, particularly 3 to 8 carbon atoms is preferable. Such silane coupling agents that do not have Y cannot be used.

_{Specifically, CF 3 (CF 2) 7} CH 2 CH 2 Si (OCH 3) 3, CF 3 CH 2 CH 2 Si (OCH 3) 3, CF 3 CF 2 CH 2 CH 2 Si (OC 3 H 7 ) ₃ , CF ₃ (CF ₂ ) ₅ CH ₂ CH ₂ Si (OCH ₃ ) ₃ , (CF ₃ ) ₂ CF (CF ₂ ) ₈ CH ₂ CH ₂ Si (OCH ₃ ) ₃ , CF ₃ (CF ₂ ) _{4 CH 2 CH 2 Si (OC 2} H 5) 3, CF 3 (CF 2) 5 CH 2 CH 2 Si (OC 2 H 5) 3, CF 3 (CF 2) 7 CH 2 CH 2 Si (OC 2 H 5 ) ₃ , CF ₃ (CF ₂ ) ₄ CH ₂ CH ₂ SiCH ₃ (OC ₂ H ₅ ) ₂ , CF ₃ (CF ₂ ) ₇ CH ₂ CH ₂ SiCH ₃ (OC ₂ H ₅ ) ₂ , CF ₃ (CF ₂₎ ) ₄ CH ₂ CH _{2 iCH 3 (OC 3 H 7)} 2, CF 3 (CF 2) 5 CH 2 CH 2 SiCH 3 (OC 3 H 7) 2, CF 3 (CF 2) 7 CH 2 CH 2 SiCH 3 (OC 3 H 7) ₂ , CF ₃ (CF ₂ ) ₂ CH ₂ CH ₂ Si (OC ₃ H ₇ ) _{3 and the} like.

  Moreover, it is preferable that the addition amount of a fluoroalkyl silane compound is 0.01-5 weight part with respect to 1 weight part of hexaboride particle | grains. More preferably, it is 0.1 to 3 parts by weight. When the addition amount of the hexaboride fine particles is less than 0.01 parts by weight, the hexaboride fine particles cannot be uniformly dispersed, which is not preferable. Further, when the amount exceeds 5 parts by weight, it is difficult to uniformly mix with the acrylic resin molding material because it does not become powdery even if the alcohol is volatilized after the acrylic resin aggregation inhibitor is added to the dispersion and mixed. This is not preferable.

(C) Anti-agglomeration agent The anti-agglomeration agent used in the present invention has a functional group that is soluble in alcohol, compatible with acrylic resin molding materials, and has an adsorption effect on the surface of hexaboride fine particles. It is an acrylic polymer compound that does not have.

  If this anti-aggregation agent is not soluble in alcohol, the hexaboride fine particles are liable to form aggregates in the powdery material, and the dispersibility becomes insufficient. Further, if the acrylic resin aggregation inhibitor is not compatible with the acrylic resin molding material, the haze (cloudiness) of the molded body using the masterbatch is increased, and the design properties are lowered. Moreover, if the acrylic resin aggregation inhibitor has a functional group having an adsorption effect on the surface of the hexaboride fine particles, it is easy to form aggregates of hexaboride particles in the acrylic resin and the dispersibility becomes insufficient. Since the haze (cloudiness) of the molded body using the master batch is increased and the design property is lowered, it is not preferable.

Specifically, the anti-aggregation agent is an acrylic such as a copolymer of (meth) acrylic acid hydroxyalkyl ester having 1 to 8 carbon atoms and (meth) acrylic acid alkyl ester having 1 to 13 carbon atoms. Based polymer compounds. An example of such an acrylic polymer compound is trade name: BR-105 (manufactured by Mitsubishi Rayon Co., Ltd.).
In the case of a (meth) acrylic acid hydroxyalkyl ester having 9 or more carbon atoms or a copolymer with a (meth) acrylic acid alkyl ester having 14 or more carbon atoms, it becomes difficult to dissolve in alcohol, Agglomerates of hexaboride fine particles are easily formed in the acrylic resin, resulting in insufficient dispersibility. The molded body using the masterbatch has excellent heat ray shielding ability, but has high haze (cloudiness). Design properties may be reduced.

  The addition amount of the aggregation inhibitor is preferably 1.0 to 50 parts by weight with respect to 1 part by weight of the hexaboride fine particles. More preferably, it is 2 to 20 parts by weight. When the addition amount of the hexaboride fine particles is less than 1.0 part by weight, the hexaboride fine particles are liable to form an aggregate in the powdery material, and the dispersibility becomes insufficient. On the other hand, when the amount exceeds 50 parts by weight, there is a concern that the mechanical strength of the molded body is lowered and the weather resistance is deteriorated when used outdoors.

(D) Acrylic resin molding material The acrylic resin molding material used in the present invention is not particularly limited as long as it is an acrylic resin used in this field.

  For example, acrylic acid ester, vinyl acetate, styrene, acrylonitrile, methacrylonitrile, etc., having methyl methacrylate, ethyl methacrylate, propyl methacrylate, butyl methacrylate, etc. as main raw materials and having an alkyl group having 1 to 8 carbon atoms as required Examples thereof include polymers or copolymers using as a copolymerization component. Further, a (meth) acrylic resin polymerized in multiple stages can also be used.

  In the present invention, in order to produce a masterbatch, first, the aggregation preventing agent (C) is added to the alcohol dispersion of the hexaboride fine particles (A), and then pulverized with a medium stirring mill to obtain the hexaboride fine particles. Next, the surface is coated, and then alcohol is volatilized to form powder, and the obtained powder is melt-kneaded with the acrylic resin molding material (D).

(1) Grinding and surface coating of 6 boride fine particles Alcohol is mixed with 6 boride particles of micron order to make a slurry. The method for coating the surface of the hexaboride fine particles is not particularly limited, but it is preferable to carry out the method simultaneously with the pulverization of the hexaboride fine particles. When the hexaboride fine particles are pulverized, a fluoroalkylsilane compound can be added and pulverized with a medium stirring mill. As a result, a dispersion containing hexaboride fine particles coated with a fluoroalkylsilane compound is obtained.
Examples of the alcohol include 2-methoxyethanol, ethanol, methanol, diacetone alcohol, and isopropyl alcohol. Preference is given to isopropyl alcohol. In addition, N, N-dimethylformamide, formamide, N-methyl-2-pyrrolidone, toluene and the like can be blended within a range not impairing the object of the present invention. The amount of the alcohol solvent used is not particularly limited, but can be 0.1 to 10 parts by weight, preferably 0.1 to 1.5 parts by weight with respect to 1 part by weight of the fluoroalkylsilane compound. .

(2) Powdering Next, after adding and mixing an aggregation inhibitor, alcohol is volatilized from the obtained liquid mixture. Various distillation and evaporation operations can be applied to this method. That is, there are a method of distilling by heating above the boiling point of alcohol under normal pressure or reduced pressure, or a method of distilling by introducing an inert gas such as nitrogen, carbon dioxide, argon or helium. Industrially, a method of heating and distilling with a solution up to 80 to 200 ° C., preferably 120 to 180 ° C. at normal pressure is suitable. The distillation time is not particularly limited but is usually 1 to 5 hours. Industrially, after raising the temperature to this range, the temperature may be maintained and maintained for 0.5 to 10 hours, preferably 1 to 5 hours to complete the reaction. Things can be obtained efficiently.

(3) Mixing of acrylic resin Then, the obtained powdery substance is mixed with an acrylic resin, this is granulated or pelletized, and other additives are blended as necessary.
When powdered or pelletized, an additive solution is added to methyl methacrylate, ethyl methacrylate, propyl methacrylate, butyl methacrylate, etc., which are the raw materials for the acrylic resin, and mixed uniformly by a known method in the same manner as suspension polymerization or lump Polymerization can also be performed by a known method such as polymerization. Thereby, a mixture in which fine particles are uniformly dispersed in an acrylic resin can be prepared.

  Other additives that can be blended include, for example, stabilizers such as hindered phenols and phosphorus, UV absorbers such as hydroxybenzophenone, salicylic acid, HALS, triazole and triazine, phosphate esters, Examples include phenolic antioxidants, coupling agents, surfactants, antistatic agents, mold release agents, and the like. The blending amount of the additive is 10% by weight or less with respect to the hexaboride fine particles and the acrylic resin component.

Next, melt kneading is performed using a melt kneading apparatus such as an extruder. For mixing and melting and kneading these components, preliminary blenders such as ribbon blenders, tumblers, nauter mixers, Henschel mixers, super mixers, planetary mixers, Banbury mixers, kneaders, rolls, kneader ruders, single screw extruders A melt-kneading apparatus such as a twin-screw extruder can be used.
The raw materials may be supplied to the melt-kneading apparatus after the respective components have been mixed in advance, and the respective components can be supplied to the melt-kneading apparatus in an independent form. A hexaboride microparticle-containing masterbatch in which the dispersibility of hexaboride microparticles in the acrylic resin molding material according to the present invention is improved by processing the melt-kneaded product thus obtained into a pellet form. Obtainable.

2. Master batch In this invention, a master batch is obtained by the said manufacturing method, melt-kneading the powdery substance containing hexaboride microparticles | fine-particles (A) and an aggregation inhibitor (C) with an acrylic resin molding material (D). It is a master batch.

The mixture obtained by mixing the powder containing hexaboride fine particles (A) and the anti-agglomeration agent (C) with the acrylic resin molding material (D) was kneaded with a vent type uniaxial or biaxial extruder. And processed into pellets. The pellets can be obtained by the most common method of cutting melt extruded strands. Accordingly, examples of the shape include a cylindrical shape and a prismatic shape. It is also possible to adopt a so-called hot cut method in which the molten extrudate is directly cut. In such a case, it is common to take a shape close to a sphere.
As described above, the masterbatch of the present invention can take any form or shape, but the thermoplastic resin used for diluting the heat-shielding component-containing masterbatch when molding a heat-shielding transparent resin molding. The same form and shape as the molding material are preferred.
The content of the hexaboride fine particles in the master batch is 0.01 to 20% by weight, preferably 0.1 to 10% by weight, based on the acrylic resin. When the content of hexaboride fine particles is less than 0.01% by weight, it depends on the thickness of the heat ray-shielding acrylic resin molding to be molded, but a film having an acrylic resin molding to be molded of 100 μm or less is sufficient. Heat ray shielding ability may not be obtained. Further, when the content exceeds 20% by weight, aggregation of the hexaboride fine particles occurs, and the dispersibility of the hexaboride fine particles in the acrylic resin becomes insufficient, so that the haze of the molded body using the masterbatch increases. This is not preferable because the designability is reduced.

3. Molded body In the molded body of the present invention, the master batch containing the acrylic resin molding material (D) is diluted and melt-kneaded with the acrylic resin of the same type or different type from the acrylic resin molding material (D). It is a molded body formed into a shape.

As the molding method, methods such as injection molding, extrusion molding, compression molding, or rotational molding can be used. In particular, injection molding and extrusion molding are preferable because they can be efficiently molded into a desired shape. As a method for obtaining a plate-shaped (sheet-shaped) or film-shaped molded body by extrusion molding, a method is adopted in which a molten acrylic resin extruded using an extruder such as a T-die is taken out while being cooled by a cooling roll.
The molding temperature varies depending on the composition of the acrylic resin used, but is heated to a temperature 50 to 150 ° C. higher than the melting point or glass transition temperature of the resin so that sufficient fluidity can be obtained. For example, it is 200 ° C. or higher, preferably 220 ° C. to 300 ° C. If it is lower than 200 ° C., the viscosity specific to the polymer cannot be lowered, and therefore, the hexaboride fine particles cannot be uniformly dispersed in the acrylic resin, which is not preferable. A temperature higher than 300 ° C. is not preferable because the acrylic resin may be decomposed and deteriorated.

4). Laminated body The laminated body of this invention is a laminated body formed by laminating | stacking the said molded object on thermoplastic resin molded objects other than an acrylic resin molding material (D). The laminate itself can be used for window materials, arcades, ceiling domes, carports and the like used for openings of building roofing materials, wall materials, automobiles, trains, airplanes and the like.

In addition, it can also be used as a structural material as a heat ray shielding transparent laminate that is laminated and integrated with other transparent molded bodies such as inorganic glass, resin glass, and resin film. For example, a heat ray shielding transparent laminated body having a heat ray shielding function and a scattering prevention function can be obtained by stacking and integrating a heat ray shielding acrylic resin molded body previously formed into a film shape on inorganic glass by a heat laminating method.
In addition, by heat lamination method, coextrusion method, press molding method, injection molding method etc., heat ray shielding transparent laminate can be obtained by laminating and integrating with other transparent molding at the same time as heat ray shielding acrylic resin molding. It is also possible. The said heat ray shielding transparent laminated body can be used as a more useful structural material by complementing a mutual fault, exhibiting the advantage which a mutual molded object has effectively.

  As described above, the masterbatch obtained by the production method of the present invention has improved dispersibility without agglomeration of hexaboride particles in an acrylic resin that has not been obtained conventionally. For this reason, the molded object using the said masterbatch has the outstanding heat ray shielding ability, and its haze is also low and favorable. In addition, since the dispersibility is good and the acrylic resin aggregation inhibitor is used, the weather resistance against rainwater received during use outdoors is also good. Therefore, excellent heat ray shielding ability for acrylic resin moldings widely used for building roofing materials, wall materials, window materials used in openings of automobiles, trains, airplanes, arcades, ceiling domes, carports, etc. In addition to being able to impart design properties, it can be used in a wide range of fields.

  Examples of the present invention will be described in detail below, but the present invention is not limited to the following examples.

  Here, optical property evaluation of the obtained molded body was performed according to JIS K 7136 using a haze meter (manufactured by Murakami Color Research Laboratory) for haze (H) (unit:%). For the visible light transmittance T (unit:%) and the solar radiation transmittance ST (unit:%), a spectrophotometer U-4000 (manufactured by Hitachi, Ltd.) was used.

(Example 1)
260 g of lanthanum hexaboride powder having a particle size of 1 to 3 μm and 1688 g of 2-propanol were mixed with stirring. Further, YRSiX ₃ (wherein Y is a fluorinated alkyl group having 1 carbon atom and R is an alkylene having 2 carbon atoms) Group, and X represents an alkoxy group having 1 carbon atom.) 52 g of a fluoroalkylsilane compound (b1): KBM-7103 (manufactured by GE Toshiba Silicones) represented by the following formula was added to prepare a slurry. This slurry was put into a medium stirring mill together with beads, and the slurry was circulated and subjected to pulverization and dispersion treatment to obtain a lanthanum hexaboride dispersion coated with a fluoroalkylsilane compound having an average particle size of 90 nm. (Hereafter, abbreviated as A liquid)
Acrylic resin aggregation inhibitor (c1) that is soluble in 2-propanol, is compatible with acrylic resin molding materials, and does not have a functional group having an adsorption effect on the surface of lanthanum hexaboride. ): 9.75 g of a liquid obtained by dissolving BR-105 (manufactured by Mitsubishi Rayon) so as to be 40% by weight (hereinafter abbreviated as B liquid) was added and mixed with 10 g of the above-mentioned A liquid. Then, 2-propanol was volatilized from the obtained mixed liquid, and a powdery material in which lanthanum hexaboride coated with a fluoroalkylsilane compound was uniformly dispersed in an acrylic resin aggregation inhibitor was obtained. This powdery substance contained 3 parts by weight of an anti-agglomeration agent with respect to 1 part by weight of lanthanum hexaboride powder.
Further, after adding the above powdery substance to the acrylic resin so that the content of lanthanum hexaboride is 0.27% by weight with respect to the acrylic resin (manufactured by Sumitomo Chemical Co., Ltd.), the mixture is uniformly mixed, and then a twin-screw extruder (Toyo The extruded strand with a diameter of 3 mm was cut into pellets to obtain a master batch mainly composed of lanthanum hexaboride and an acrylic resin.
Furthermore, after mixing the above master batch uniformly with an acrylic resin (manufactured by Sumitomo Chemical Co., Ltd.) so that the content of lanthanum hexaboride is 0.006% by weight, T-die is produced by an injection molding machine (manufactured by Toyo Seiki Seisakusho). Was used to obtain a sheet-like molded body having a thickness of 10 cm × 5 cm and a thickness of 2.0 mm.
The obtained molded article was evaluated for optical properties: haze (H), visible light transmittance T (unit:%), and solar radiation transmittance ST (unit:%). The evaluation results are shown in Table 1. Further, the dispersion state of lanthanum hexaboride in the obtained molded body was observed using a transmission electron microscope (manufactured by Hitachi, Ltd.). The observation results are shown in FIG. It can be confirmed that the lanthanum hexaboride in the sheet-like molded body is dispersed without agglomeration.

(Example 2)
3.9 g of the B solution was added to and mixed with 10 g of the A solution, and a powdery material was obtained in the same manner as in Example 1. This powdery substance contains 0.9 part by weight of the aggregation inhibitor (C) with respect to 1 part by weight of lanthanum hexaboride (A). Furthermore, a sheet-like molded body was obtained in the same manner as in Example 1 using the powdery product. The evaluation results are shown in Table 1.

(Example 3)
178g of said B liquid was added and mixed with 10g of said A liquid, and the powdery material was obtained by the method similar to Example 1. This powdery substance contains 55 parts by weight of the aggregation inhibitor (C) with respect to 1 part by weight of lanthanum hexaboride (A). Furthermore, a sheet-like molded body was obtained in the same manner as in Example 1 using the powdery product. The evaluation results are shown in Table 1.

Example 4
A sheet was obtained in the same manner as in Example 1 except that the powdery substance described in Example 1 was added to the acrylic resin (Sumitomo Chemical Co., Ltd.) so that the content of lanthanum hexaboride was 0.01% by weight. A shaped molded body was obtained. The evaluation results are shown in Table 1.

(Example 5)
Sheet-like molding in the same manner as in Example 1 except that the powdery substance described in Example 1 was added to acrylic resin (Sumitomo Chemical Co., Ltd.) so that the content of lanthanum hexaboride was 20% by weight. Got the body. The evaluation results are shown in Table 1.

(Comparative Example 1)
An acrylic resin aggregation inhibitor (c2) that is compatible with the acrylic resin molding material and does not have a functional group having an adsorption effect on the surface of lanthanum hexaboride but is insoluble in 2-propanol A sheet-like molded body was obtained in the same manner as in Example 1 except that BR-87 (manufactured by Mitsubishi Rayon) was used.
Regarding the evaluation of the optical properties of the obtained molded body, the same equipment as in Example 1 was used for evaluation. The evaluation results are shown in Table 1.

(Comparative Example 2)
A sheet-like molded body was obtained in the same manner as in Example 1 except that the fluoroalkylsilane compound (b1) was not added.
The optical characteristics of the obtained molded body were evaluated using the same equipment as in Example 1. The evaluation results are shown in Table 1.
Further, the dispersion state of lanthanum hexaboride in the obtained molded body was also observed using the same equipment as in Example 1. The observation results are shown in FIG. Since no fluoroalkylsilane compound is added, it can be confirmed that the lanthanum hexaboride in the sheet-like molded body is partially aggregated.

(Comparative Example 3)
A sheet-like molded body was obtained in the same manner as in Example 1 except that methylmethoxysilane (b2) was added instead of the fluoroalkylsilane compound (b1).
The optical characteristics of the obtained molded body were evaluated using the same equipment as in Example 1. The evaluation results are shown in Table 1.

It is a transmission electron microscope observation photograph which shows the dispersion state of the lanthanum hexaboride in the sheet-like molded object obtained by this invention. It is a transmission electron microscope observation photograph which shows the dispersion state of the lanthanum hexaboride in the sheet-like molded object for comparison to which a fluoroalkylsilane compound is not added.

Claims (12)

After adding the coagulation inhibitor (C) to the alcohol dispersion of the hexaboride fine particles (A), the alcohol is volatilized, and the obtained powder is melt-kneaded with the acrylic resin molding material (D). A method for producing a batch, comprising:
The hexaboride fine particles (A) are surface-coated with the fluoroalkylsilane compound (B), while the aggregation inhibitor (C) is soluble in alcohol and compatible with the acrylic resin molding material (D). And an acrylic polymer compound having no functional group adsorbed on the surface of the hexaboride fine particles (A). The hexaboride fine particles (A) are represented by the general formula XB ₆ (wherein the element X is La, Ce, Pr, Nd, Gd, Tb, Dy, Ho, Y, Sm, Eu, Er, Tm, Yb, Lu, The method for producing a masterbatch according to claim 1, which is a hexaboride represented by at least one selected from Sr and Ca.   The method for producing a masterbatch according to claim 1, wherein the average particle diameter of the hexaboride fine particles (A) is 500 nm or less.   The hexaboride fine particles (A) are obtained by dispersing hexaboride particles having an average particle diameter of 1 μm or more in alcohol, adding the fluoroalkylsilane compound (B) to the slurry, and then pulverizing the mixture with a medium stirring mill. The manufacturing method of the masterbatch of Claim 1 characterized by these.   The content of hexaboride fine particles (A) is 0.01 to 20 parts by weight with respect to 100 parts by weight of the acrylic resin molding material (D). Manufacturing method of masterbatch. The method for producing a masterbatch according to claim 1, wherein the fluoroalkylsilane compound (B) is represented by the following general formula (1).
YRSiX ₃ (1)
(In the formula, Y represents a fluorinated alkyl group having 1 to 12 carbon atoms, R represents an alkylene group having 2 to 4 carbon atoms, and X represents an alkoxy group having 1 to 4 carbon atoms.)   The method for producing a masterbatch according to claim 1, wherein the addition amount of the fluoroalkylsilane compound (B) is 0.01 to 5 parts by weight with respect to 1 part by weight of hexaboride particles.   The acrylic polymer compound of the aggregation inhibitor (C) is a copolymer of a C1-C8 (meth) acrylic acid hydroxyalkyl ester and a C1-C13 (meth) acrylic acid alkyl ester. The manufacturing method of the masterbatch of Claim 1 characterized by these.   The method for producing a masterbatch according to claim 1, wherein the addition amount of the aggregation inhibitor (C) is 1.0 to 50 parts by weight per 1 part by weight of hexaboride particles.   A powdery product obtained by the production method according to claim 1 and containing hexaboride fine particles (A) and an anti-aggregation agent (C) is melt-kneaded with an acrylic resin molding material (D). Master batch.   A master batch containing the acrylic resin molding material (D) according to claim 10 is diluted and melt-kneaded with the same or different type of acrylic resin as the acrylic resin molding material (D), and then molded into a predetermined shape. A formed body.   The laminated body by which the molded object of Claim 11 is laminated | stacked on thermoplastic resin molded objects other than an acrylic resin molding material (D).

Images