CN112513176B - Resin molded body, heat ray shielding plate, ceiling material, and window material - Google Patents

Resin molded body, heat ray shielding plate, ceiling material, and window material Download PDF

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Publication number
CN112513176B
CN112513176B CN201980050352.9A CN201980050352A CN112513176B CN 112513176 B CN112513176 B CN 112513176B CN 201980050352 A CN201980050352 A CN 201980050352A CN 112513176 B CN112513176 B CN 112513176B
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particles
resin molded
tungsten oxide
dispersant
molded article
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CN112513176A (en
Inventor
桑原彩香
小野雅彦
铃木正法
渡边博之
平冈沙纪
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Mitsubishi Chemical Corp
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Mitsubishi Chemical Corp
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/20—Oxides; Hydroxides
    • C08K3/22—Oxides; Hydroxides of metals
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K9/00—Use of pretreated ingredients
    • C08K9/12—Adsorbed ingredients, e.g. ingredients on carriers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L33/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
    • C08L33/04—Homopolymers or copolymers of esters
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L51/00—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
    • C08L51/04—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers grafted on to rubbers
    • E—FIXED CONSTRUCTIONS
    • E04—BUILDING
    • E04D—ROOF COVERINGS; SKY-LIGHTS; GUTTERS; ROOF-WORKING TOOLS
    • E04D13/00—Special arrangements or devices in connection with roof coverings; Protection against birds; Roof drainage; Sky-lights
    • E04D13/16—Insulating devices or arrangements in so far as the roof covering is concerned, e.g. characterised by the material or composition of the roof insulating material or its integration in the roof structure
    • E—FIXED CONSTRUCTIONS
    • E06—DOORS, WINDOWS, SHUTTERS, OR ROLLER BLINDS IN GENERAL; LADDERS
    • E06B—FIXED OR MOVABLE CLOSURES FOR OPENINGS IN BUILDINGS, VEHICLES, FENCES OR LIKE ENCLOSURES IN GENERAL, e.g. DOORS, WINDOWS, BLINDS, GATES
    • E06B5/00—Doors, windows, or like closures for special purposes; Border constructions therefor

Abstract

The invention provides a resin molded body with excellent transparency, low coloring property and heat ray shielding property; a heat ray shielding plate, a ceiling material, and a window material comprising the resin molded body. A resin molded article which is formed from a resin composition containing a transparent resin, tungsten oxide particles (W), and dispersant particles (X), and which contains composite particles (XW) having at least one of a form in which the tungsten oxide particles (W) are present on the particle surfaces of the dispersant particles (X) and a form in which a plurality of tungsten oxide particles (W) are contained inside the particles of the dispersant particles (X); and a resin molded body which is formed from a resin composition containing a transparent resin, tungsten oxide particles (W) and dispersant particles (X), and which contains composite particles (XW) containing the tungsten oxide particles (W) and the dispersant particles (X), wherein the composite particles (XW) have a dispersed particle diameter of 100nm to 1000 nm.

Description

Resin molded body, heat ray shielding plate, ceiling material, and window material
Technical Field
The present invention relates to a resin molded body, a heat ray shielding plate, a ceiling material, and a window material.
The present application claims priority based on Japanese patent application No. 2018-143463 at 31 in 7 months of 2018, japanese patent application No. 2018-143464 at 31 in 7 months of 2018 and Japanese patent application No. 2019-048389 at 15 in 3 months of 2019, the contents of which are incorporated herein by reference.
Background
Ceiling materials and window materials for buildings, automobiles, trains, buses, and the like, and protective materials for lighting devices, billboards, and the like are required to be transparent and have low sense of existence in terms of design. That is, there is an increasing demand for resin molded articles having high transparency in the visible light range and suppressed coloration.
The ceiling material, the window material, the protective material for lighting devices, billboards, and the like are required to have a property of blocking light (hereinafter, referred to as "heat ray shielding property") in an infrared ray region included in light from a light source such as sunlight, a fluorescent lamp, and a lamp (hereinafter, referred to as "heat ray shielding property"). In recent years, there has been an increasing demand for resin molded articles excellent in heat ray shielding properties.
As a technique for improving transparency, low coloring property, and heat ray shielding property of a resin molded body, for example, patent document 1 discloses a resin molded body containing a composite tungsten oxide surface-coated with a polymer compound having an ester group.
Patent document 2 discloses a heat-ray-shielding microparticle-containing resin composition containing composite tungsten oxide microparticles, an acrylic resin-based dispersant having an amino group as a functional group, and an acrylic resin-based dispersant having a hydroxyl group or a carboxyl group as a functional group.
Patent document 3 discloses a heat-ray-shielding transparent resin molded article obtained by dispersing (composite) tungsten oxide fine particles in an acrylic resin with a high heat-resistant dispersant having an acrylic main chain and a hydroxyl group or an epoxy group.
Patent document 4 discloses a heat ray shielding film in which the content of the composite tungsten oxide particles of the heat ray shielding film per unit area of the projected area is specified.
Prior art literature
Patent literature
Patent document 1 Japanese patent laid-open publication No. 2010-168430
Patent document 2 Japanese patent application laid-open No. 2014-231439
Patent document 3 Japanese patent laid-open No. 2008-24902
Patent document 4 International publication No. 2016/021336
Disclosure of Invention
Problems to be solved by the invention
However, in the resin compositions, resin molded articles, and heat ray shielding films disclosed in patent documents 1 to 4, tungsten oxide particles are aggregated and the haze value is increased, and therefore, transparency is insufficient and coloring is also large. Further, the resin molded article is required to have excellent heat ray shielding properties.
The present invention aims to solve these problems. That is, an object of the present invention is to provide a resin molded body excellent in transparency, low coloring property and heat ray shielding property; a heat ray shielding plate, a ceiling material, and a window material comprising the resin molded body.
Means for solving the problems
The present invention relates to the following [1] to [25].
[1] A resin molded article comprising a resin composition containing a transparent resin, tungsten oxide particles (W) and dispersant particles (X), wherein the resin molded article comprises composite particles (XW) having at least one of a form in which the tungsten oxide particles (W) are present on the particle surfaces of the dispersant particles (X) and a form in which a plurality of tungsten oxide particles (W) are contained in the particles of the dispersant particles (X).
[2] A resin molded article comprising a resin composition containing a transparent resin, tungsten oxide particles (W) and dispersant particles (X), wherein the resin composition contains composite particles (XW) containing the tungsten oxide particles (W) and the dispersant particles (X), and the composite particles (XW) have a dispersed particle diameter of 100nm to 1000 nm.
[3] The resin molded article according to [2], wherein the composite particles (XW) have at least one of a form in which tungsten oxide particles (W) are present on the particle surfaces of the dispersant particles (X) and a form in which a plurality of tungsten oxide particles (W) are contained in the particles of the dispersant particles (X).
[4]According to [1]]～[3]The resin molded article according to any one of the above, wherein the tungsten oxide particles (W) are contained in an amount of 0.05g/m per unit area of the projected area of the resin molded article 2 Above 3.00g/m 2 The following is given.
[5] The resin molded article according to any one of [1] to [4], wherein the transparent resin is a (meth) acrylic polymer (P), and the resin composition is a (meth) acrylic resin composition.
[6]A resin molded article comprising a (meth) acrylic resin composition comprising a (meth) acrylic polymer (P), tungsten oxide particles (W) and dispersant particles (X), the resin molded article comprising composite particles (XW) having at least one of a form in which the tungsten oxide particles (W) are adsorbed on the particle surfaces of the dispersant particles (X) and a form in which a plurality of tungsten oxide particles (W) are contained in the particle surfaces of the dispersant particles (X), the content of the tungsten oxide particles (W) in the resin molded article per unit area of the projected area of the resin molded article being 0.05g/m 2 Above 3.00g/m 2 The following is given.
[7] The resin molded article according to any one of [1] to [6], wherein the dispersant particles (X) are the particle-shaped copolymer (D) having a crosslinked structure, and the composite particles (XW) contain composite particles (XW 1) in which the tungsten oxide particles (W) are present on the particle surfaces of the dispersant particles (X).
[8] A resin molded article comprising a (meth) acrylic resin composition containing a (meth) acrylic polymer (P), tungsten oxide particles (W) and dispersant particles (X), wherein the dispersant particles (X) are a particulate copolymer (D) having a crosslinked structure, and composite particles (XW 1) are formed by adsorbing the tungsten oxide particles (W) onto the particle surfaces of the dispersant particles (X).
[9] The resin molded article according to [7] or [8], wherein the particulate copolymer (D) is a multistage polymerized copolymer comprising: rubbery copolymer having a crosslinked structure; and an outer polymer (C) obtained by polymerizing a monomer mixture containing at least one of an alkyl acrylate (a 1) having an alkyl group having 1 to 8 carbon atoms and an alkyl methacrylate (a 2) having an alkyl group having 1 to 8 carbon atoms in the presence of the rubber-like copolymer.
[10] The resin molded article according to [9], wherein the rubbery copolymer comprises an intermediate layer polymer (B) obtained by polymerizing a monomer mixture comprising an alkyl acrylate (a 1) having an alkyl group having 1 to 8 carbon atoms, an aromatic vinyl compound (a 3) and a polyfunctional monomer (a 5).
[11] The resin molded article according to [9] or [10], wherein the rubber-like copolymer comprises: an innermost polymer (A) obtained by polymerizing a monomer mixture containing an alkyl acrylate (a 1) having an alkyl group having 1 to 8 carbon atoms, an alkyl methacrylate (a 4) having an alkyl group having 1 to 4 carbon atoms, an aromatic vinyl compound (a 3), and a polyfunctional monomer (a 5); and an intermediate layer polymer (B) obtained by polymerizing a monomer mixture containing an alkyl acrylate (a 1) having an alkyl group having 1 to 8 carbon atoms, an aromatic vinyl compound (a 3), and a polyfunctional monomer (a 5) in the presence of the innermost layer polymer (A).
[12] The resin molded article according to any one of [6] to [11], wherein the composite particles (XW) in the (meth) acrylic resin composition have a dispersed particle diameter of 100nm to 1000 nm.
[13] The resin molded article according to any one of [1] to [6], wherein the dispersant particles (X) are a particulate copolymer containing a repeating unit derived from an alkyl (meth) acrylate (excluding methyl methacrylate) having an alkyl group having 1 to 8 carbon atoms as an ester side chain, and the content W (unit: mass ppm) of the tungsten oxide particles (W) and the content X (unit: mass ppm) of the dispersant particles (X) contained in the resin molded article satisfy the following formulas (3) and (4).
50≤w≤500 (3)
5.11w+444≤x≤10.00w+2000 (4)
[14] A resin molded article comprising a (meth) acrylic resin composition containing a (meth) acrylic polymer (P), tungsten oxide particles (W) and dispersant particles (X), wherein the dispersant particles (X) are a particulate copolymer containing a repeating unit derived from an alkyl (meth) acrylate having an alkyl group having 1 to 8 carbon atoms as an ester side chain (excluding methyl methacrylate), and contain composite particles (XW) having at least one of a form in which the tungsten oxide particles (W) are adsorbed onto the particle surfaces of the dispersant particles (X) and a form in which the dispersant particles (X) contain a plurality of tungsten oxide particles (W) within the particles of the dispersant particles (X), and the content W (unit: mass ppm) of the tungsten oxide particles (W) and the content X (unit: mass ppm) of the dispersant particles (X) contained in the resin molded article satisfy the following formulas (3) and (4).
50≤w≤500 (3)
5.11w+444≤x≤10.00w+2000 (4)
[15] The resin molded article according to [13] or [14], wherein the content W (unit: mass ppm) of tungsten oxide particles (W) and the content X (unit: mass ppm) of dispersant particles (X) contained in the resin molded article satisfy the following formulas (5) and (6).
60≤w≤450 (5)
5.38w+477≤x≤7.00w+1150 (6)
[16] The resin molded article according to any one of [13] to [15], wherein the composite particles (XW) in the (meth) acrylic resin composition have a dispersed particle diameter of 100nm to 1000 nm.
[17] The resin molded article according to any one of [13] to [16], wherein the dispersant particle (X) is a copolymer (X2-A) comprising at least one of a repeating unit derived from an alkyl acrylate (a 7) having an alkyl group having 2 to 8 carbon atoms as an ester side chain and a repeating unit derived from an alkyl methacrylate (a 8) having an alkyl group having 2 to 8 carbon atoms as an ester side chain, and having a glass transition temperature (Tg) of 10 ℃ to 40 ℃.
[18] The resin molded article according to [17], wherein the copolymer (X2-A) contains 25 to 45 mass% of the repeating unit derived from the alkyl acrylate (a 7) and 10 to 30 mass% of the repeating unit derived from the alkyl methacrylate (a 8) based on the total mass of the copolymer (X2-A).
[19] The resin molded body according to [17] or [18], wherein the alkyl acrylate (a 7) contains at least 1 selected from the group consisting of ethyl acrylate, n-propyl acrylate, n-butyl acrylate and 2-ethylhexyl acrylate.
[20] The resin molded article according to any one of [17] to [19], wherein the alkyl methacrylate (a 8) contains at least one of n-butyl methacrylate and isobutyl methacrylate.
[21] The resin molded article according to any one of [1] to [20], wherein the composite particles (XW) are dispersed in the (meth) acrylic resin composition substantially in a one-time dispersion.
[22] A resin molded article comprising a resin composition containing a transparent resin, tungsten oxide particles (W) and dispersant particles (X),
the composite particles (XW) having at least one of a form in which tungsten oxide particles (W) are present on the particle surface of the dispersant particles (X) and a form in which a plurality of tungsten oxide particles (W) are contained in the particles of the dispersant particles (X), and having a total light transmittance of 60% or more as measured in accordance with JIS K7361-1 in the wavelength range of 380 to 780nm, a haze of 10% or less as measured in accordance with JIS K7136 in the wavelength range of 380 to 780nm, a Yellow Index (YI) of less than 4.0 in the thickness direction as measured in accordance with ASTM D1925, and a heat ray blocking rate (thermal in-use) of 40% or more as measured in the wavelength range of 780 to 2100 nm.
[23] A heat ray shielding plate comprising the resin molded body of any one of [1] to [22 ].
[24] A ceiling material comprising the resin molded body of any one of [1] to [22 ].
[25] A window material comprising the resin molded body of any one of [1] to [22 ].
Effects of the invention
According to the present invention, a resin molded body excellent in transparency, low coloring property and heat ray shielding property can be provided; a heat ray shielding plate, a ceiling material, and a window material comprising the resin molded body.
Drawings
Fig. 1 is a photograph of the resin molded body of example 1 taken with a TEM.
Fig. 2 is a photograph of the resin molded body of comparative example 1 taken by TEM.
FIG. 3 is a photograph of the resin molded articles of examples 16 to 22 and comparative examples 8 to 10 taken by TEM.
Fig. 4 is a schematic diagram showing the range of the content W of tungsten oxide particles (W) and the content X of dispersant particles (X) in the resin molded body, and examples 16 to 22 and comparative examples 8 and 9.
Detailed Description
The present invention will be described in detail below.
In the present invention, "(meth) acrylic" means at least 1 selected from "acrylic" and "methacrylic".
In the present invention, "monomer" means an unpolymerized compound, and "repeating unit" means a unit derived from a monomer formed by polymerization of the monomer. The repeating unit may be a unit directly formed by polymerization reaction, or may be a unit in which a part of the unit is converted into another structure by treatment of a polymer.
In the present invention, "mass%" means the content of a specific component contained in 100 mass% of the total amount.
In the present invention, unless otherwise specified, the numerical ranges indicated by "to" are ranges including the numerical values described before and after "to" as the lower limit value and the upper limit value, and "a to B" are a to B.
< resin molded article >)
The resin molded article of the present invention is a resin molded article obtained by molding the resin composition of the present invention described later, and is a resin molded article obtained from the resin composition.
The first embodiment of the present invention is characterized by containing composite particles (XW) having at least one of a form in which tungsten oxide particles (W) are present on the particle surfaces of dispersant particles (X) and a form in which a plurality of tungsten oxide particles (W) are contained inside the particles of dispersant particles (X).
The second embodiment of the present invention is characterized by comprising composite particles (XW) comprising the tungsten oxide particles (W) and the dispersant particles (X), wherein the composite particles (XW) have a dispersed particle diameter of 100nm to 1000 nm.
The third embodiment of the present invention is characterized by comprising composite particles (XW) having at least one of a form in which tungsten oxide particles (W) are present on the particle surfaces of dispersant particles (X) and a form in which a plurality of tungsten oxide particles (W) are contained in the particle interior of dispersant particles (X), wherein the content of the tungsten oxide particles (W) in the resin molded article is 0.05g/m per unit area of the projected area of the resin molded article 2 Above 3.00g/m 2 The following is given.
In a fourth embodiment of the present invention, the dispersant particles (X) are a particulate copolymer (D) having a crosslinked structure, and composite particles (XW 1) are formed by the presence of the tungsten oxide particles (W) on the particle surfaces of the dispersant particles (X).
In a fifth embodiment of the present invention, the (meth) acrylic resin composition contains composite particles (XW) described later, the dispersant particles (X) are a particulate copolymer containing a repeating unit derived from an alkyl (meth) acrylate having an alkyl group having 1 to 8 carbon atoms as an ester side chain (except methyl methacrylate), and the relationship between the content W (unit: mass ppm) of tungsten oxide particles (W) and the content X (unit: mass ppm) of dispersant particles (X) contained in the resin molded article satisfies the specific conditions described later.
In a sixth embodiment of the present invention, the resin composition contains composite particles (XW) described later, has a total light transmittance of 60% or more measured in a wavelength range of 380 to 780nm according to JIS K7361-1, a haze of 10% or less measured in a wavelength range of 380 to 780nm according to JIS K7136, a Yellow Index (YI) in a thickness direction of less than 4.0 measured in accordance with ASTM D1925, and a heat ray blocking rate of 40% or more measured in a wavelength range of 780 to 2100 nm.
The composite particles (XW) have at least one of a form in which 1 or more tungsten oxide particles (W) are present on the particle surfaces of the dispersant particles (X) and a form in which a plurality of tungsten oxide particles (W) are contained in the particle surfaces of the dispersant particles (X). The tungsten oxide particles (W) may be present on both the particle surface and the particle interior of the dispersant particles (X). When tungsten oxide particles (W) are present on both the particle surface and the inside of the dispersant particles (X), the tungsten oxide particles (W) are included in the form of being present on the particle surface of the dispersant particles (X). Preferably, a plurality of tungsten oxide particles (W) are present on the particle surfaces of the dispersant particles (X).
In the present invention, whether or not the composite particles (XW) have these forms can be determined by, for example, observation images obtained by an electron microscope such as a TEM (Transmission Electron Microscope ).
According to the studies by the present inventors, the following tendency is found: the smaller the dispersion particle diameter (particle diameter of particles dispersed in the resin molded body) of the composite particles (XW) contained in the resin molded body, the more light having a shorter wavelength in the incident visible light wavelength region is scattered by the composite particles (XW), resulting in greater coloration of the resin molded body. On the other hand, the following tendencies were found: the larger the dispersion particle diameter of the composite particles (XW), the lower the transparency of the resin molded body, and the greater the coloration. In addition, the following trends were found: the higher the content ratio of tungsten oxide particles (W) in the resin molded article, the higher the heat ray shielding property, but the lower the transparency of the resin molded article, the greater the coloring.
Accordingly, the present inventors have further studied and found that: by containing the tungsten oxide particles (W) in the form of the composite particles (XW), the tungsten oxide particles (W) can be contained in a properly dispersed state without agglomerating them, and therefore the heat ray shielding property of the resin molded article is not impaired, and the transparency and low coloring property are improved. The composite particles (XW) need not be spherical, and the shape is not particularly limited.
The lower limit of the dispersion particle diameter of the composite particles (XW) is preferably 100nm or more, from the viewpoint that the re-aggregation of the tungsten oxide particles (W) in the resin molded body can be suppressed, the haze value of the resin molded body is reduced, and the transparency of the resin molded body becomes good. More preferably 120nm or more, still more preferably 150nm or more. The upper limit of the dispersion particle diameter of the composite particles (XW) is preferably 1000nm or less from the viewpoint of a reduction in haze value of the resin molded article and a satisfactory transparency of the resin molded article. More preferably 600nm or less, still more preferably 400nm or less. The upper limit value and the lower limit value may be arbitrarily combined.
In the present specification, the term "dispersed particle diameter of tungsten oxide particles (W)" refers to an average value of maximum particle diameters of primary particle diameters of tungsten oxide particles (W) or secondary particle diameters of agglomerated particles (maximum particle diameter refers to secondary particle diameters in the case of agglomeration and primary particle diameters in the case of non-agglomeration), and is different from the dispersed particle diameter of composite particles (XW) described later. The aggregated particles of the tungsten oxide particles (W) are secondary particles formed by contacting the tungsten oxide particles (W) (primary particles). The method for measuring the dispersion particle diameter can be measured by the same method as the method for measuring the dispersion particle diameter of the composite particles described later.
In the resin molded body of the present invention, from the viewpoint of improving the heat ray shielding property of the resin molded bodyThe projected area of the resin molded body per unit area (unit: m 2 ) The content of tungsten oxide particles (W) (hereinafter referred to as "content of tungsten oxide particles (W) per unit area"). ) The lower limit of (2) is preferably 0.05g/m 2 The above. More preferably 0.15g/m 2 The above is more preferably 0.30g/m 2 The above. On the other hand, the upper limit of the content is preferably 3.00g/m from the viewpoint of maintaining the transparency and low colorability of the resin molded product satisfactorily 2 The following is given. More preferably 2.00g/m 2 Hereinafter, it is more preferably 1.50g/m 2 The following is given. The upper limit value and the lower limit value may be arbitrarily combined.
Further alternatively, the content of tungsten oxide particles (W) per unit area of the resin molded body of the present invention is preferably 0.05g/m 2 Above 3.00g/m 2 The following is given. More preferably 0.15g/m 2 Above 2.00g/m 2 Hereinafter, it is more preferably 0.30g/m 2 Above 1.50g/m 2 The following is given.
In the present invention, the projected area of the resin molded body is an area when the resin molded body is projected on a plane, that is, a two-dimensional plane area when the resin molded body is viewed from a direction substantially perpendicular to the main plane. When the principal plane of the resin molded body has a curved surface shape or a complex concave-convex shape, the projected area of the resin molded body is smaller than the developed area of the actual molded body.
In the case where the projected area of the resin molded body is small, for example, the tungsten oxide particle (W) content per 1 square centimeter may be converted to the tungsten oxide particle (W) content per 1 square meter.
Further, from the viewpoint of improving the transparency, low coloring property, and heat ray shielding property of the resin molded product, the composite particles (XW) are preferably dispersed in the (meth) acrylic resin composition forming the resin molded product in a substantially once dispersed form. By "dispersed substantially in a once dispersed form" is meant that the proportion of primary particles of the composite particles (XW) to the whole form of agglomerated particles is 5% or less.
< resin composition >
The resin molded article of the present invention is formed from a resin composition (hereinafter referred to as "the resin composition of the present invention"). The resin composition of the present invention contains a transparent resin (described later), tungsten oxide particles (W) described later, and dispersant particles (X) described later.
The resin composition of the present invention contains a transparent resin, and thus the transparency of a resin molded article obtained by molding the resin composition is improved.
When the resin composition of the present invention contains tungsten oxide particles (W), the heat ray shielding property of the resin molded article is improved.
When the resin composition of the present invention contains the dispersant particles (X), the transparency and low coloring property of the resin molded article are improved.
Further, by containing the composite particles (XW), the resin composition of the present invention can provide a resin molded article having excellent transparency, low coloring property and heat ray shielding property.
The type of the transparent resin of the present invention is not particularly limited as long as the light transmittance in the visible light region is high. Examples of the type of the transparent resin of the present invention include resins having a total light transmittance of 60% or more as measured in accordance with JIS K7361-1 in the wavelength range of 380 to 780 nm. Specifically, 1 kind selected from the resins exemplified by (meth) acrylic resins, polycarbonate resins, polystyrene resins, and methyl methacrylate-styrene resins (MS resins) may be used alone according to desired characteristics, or 2 or more kinds may be used in combination. Among them, polycarbonate resins are preferable in terms of heat resistance and impact resistance; from the viewpoints of transparency and weather resistance, (meth) acrylic resins are preferable. One embodiment of the (meth) acrylic resin includes a (meth) acrylic polymer (P) described below.
The type of the resin composition of the present invention is not particularly limited as long as the light transmittance in the visible light region is high. Examples of the type of the resin composition of the present invention include resin compositions having a total light transmittance of 60% or more as measured in accordance with JIS K7361-1 in the wavelength range of 380 to 780 nm. Specifically, 1 kind selected from transparent resin compositions exemplified by (meth) acrylic resin compositions, polycarbonate resin compositions, polystyrene resin compositions, and methyl methacrylate-styrene resin (MS resin) compositions described later may be used alone according to desired characteristics, or 2 or more kinds may be used in combination. Among them, a polycarbonate resin composition is preferable in terms of heat resistance and impact resistance; the (meth) acrylic resin composition is preferable in terms of transparency and weather resistance.
(meth) acrylic resin composition
In the present invention, the (meth) acrylic resin composition contains a (meth) acrylic polymer (P) described later, tungsten oxide particles (W) described later, and dispersant particles (X) described later as transparent resins.
The (meth) acrylic resin composition contains the (meth) acrylic polymer (P), and thus the transparency of the resin molded article obtained by molding the (meth) acrylic resin composition is improved.
When the (meth) acrylic resin composition contains tungsten oxide particles (W), the heat ray shielding property of the resin molded article is improved.
By containing the dispersant particles (X) in the (meth) acrylic resin composition, the transparency, low coloring property and heat ray shielding property of the resin molded article become better.
Further, when the (meth) acrylic resin composition contains the composite particles (XW), the transparency, low coloring property and heat ray shielding property of the resin molded article become better.
Polycarbonate resin composition
As the polycarbonate resin composition, there may be mentioned a resin composition containing, for example, a polycarbonate resin obtained by reacting a known dihydric phenol with a known carbonylation agent by an interfacial polycondensation method, a melt transesterification method or the like, a polycarbonate resin obtained by polymerizing a known carbonate prepolymer by a solid-phase transesterification method or the like, or a polycarbonate resin obtained by polymerizing a known cyclic carbonate compound by a ring-opening polymerization method, in an amount of 80 mass% or more relative to the total mass.
Examples of the commercial products of the polycarbonate resin include Panlite series (trade name, manufactured by Di Kagaku Co., ltd.), iupilon series (trade name, manufactured by Mitsubishi engineering plastics Co., ltd.), SD POLYCA series (trade name, manufactured by Zhenku polycarbonate Co., ltd.), APEC series (trade name, manufactured by Kogyo Japan Co., ltd.), and the like.
Polystyrene resin composition
As the polystyrene resin composition, a resin composition containing a homopolymer of styrene (hereinafter abbreviated as "St") or a styrene copolymer (hereinafter abbreviated as "polystyrene resin") having a content of repeating units derived from St (hereinafter abbreviated as "St unit") of 70 mass% or more and less than 100 mass% relative to the total mass of the polystyrene resin as a transparent resin is exemplified.
Specific examples of the polystyrene resin include polystyrene resin, styrene-acrylonitrile resin, acrylonitrile-butadiene-styrene resin, and methyl methacrylate-styrene resin (MS resin). Methyl methacrylate-styrene resins are preferred.
As a commercially available product of the polystyrene resin, PSJ polystyrene (trade name, manufactured by PS Japan Co., ltd.) is exemplified.
Commercially available MS resins include Estyrene MS series (trade name, manufactured by Nitro chemical materials Co., ltd.), cevia MAS series (trade name, manufactured by Daxiu cellulo Polymer Co., ltd.).
< resin molded body (1) >)
The resin molded body (1) is an example of the resin molded body of the present invention.
In the resin molded article (1), the dispersant particles (X) are a particulate copolymer (D) having a crosslinked structure (hereinafter referred to as "dispersant particles (X1)").
In the resin molded article (1), the composite particles (XW) have a morphology in which tungsten oxide particles (W) are present on the particle surfaces of dispersant particles (X1) described later (hereinafter referred to as "composite particles (XW 1)").
The resin molded article (1) can satisfy the following formulas (1) and (2) when the content of tungsten oxide particles (W) in the resin molded article (1) is W (unit: mass ppm) and the content of dispersant particles (X1) is X (unit: mass ppm).
4≤w≤13000 (1)
50≤x≤20000 (2)
In the resin molded body (1), the lower limit of the content W of the tungsten oxide particles (W) is not particularly limited, and is preferably 4 mass ppm or more from the viewpoint of improving the heat ray shielding property of the resin molded body. More preferably 50 mass ppm or more, still more preferably 60 mass ppm or more, and particularly preferably 100 mass ppm or more. On the other hand, the upper limit of the content W of the tungsten oxide particles (W) is not particularly limited, but is preferably 13000 mass ppm or less from the viewpoint of being able to maintain the transparency and low colorability of the resin molded article satisfactorily. More preferably 600 mass ppm or less, still more preferably 500 mass ppm or less, particularly preferably 450 mass ppm or less. The upper and lower limits mentioned above may be combined arbitrarily.
In the resin molded article (1), the lower limit of the content X of the dispersant particles (X1) is not particularly limited, but is preferably 50 mass ppm or more from the viewpoint of improving the transparency and low coloring property of the resin molded article. More preferably 500 mass ppm or more, still more preferably 1000 mass ppm or more, and particularly preferably 1500 mass ppm or more. On the other hand, the upper limit of the content X of the dispersant particles (X1) is not particularly limited, but is preferably 20000 mass ppm or less from the viewpoint of being able to maintain the transparency and low coloring property of the resin molded product satisfactorily. More preferably 10000 mass ppm or less, still more preferably 8000 mass ppm or less, and particularly preferably 6000 mass ppm or less. The upper and lower limits mentioned above may be combined arbitrarily.
In the resin molded body (1), the composite particles (XW 1) preferably have a form in which tungsten oxide particles (W) are substantially adsorbed on the particle surfaces of the dispersant particles (X1) or a form in which tungsten oxide particles are present on the particle surfaces of the dispersant particles (X1) from the viewpoint of improving the transparency, low coloring property, and heat ray shielding property of the resin molded body (1). The term "a form in which the tungsten oxide particles (W) are substantially adsorbed on the particle surfaces of the dispersant particles (X1) or a form in which the tungsten oxide particles (W) are present on the particle surfaces of the dispersant particles (X1)" means that the proportion of the form in which the plurality of tungsten oxide particles (W) are contained in the particles of the dispersant particles (X1) to the total is 10% or less.
The dispersant particles (X1) may be mixed with the transparent resin after the dispersant particles (X1) are attached to the tungsten oxide particles (W) by adsorption or the like, the transparent resin, the tungsten oxide particles (W) and the dispersant particles (X1) may be mixed at the same time, or the dispersant particles (X1) may be added to and mixed with the mixture of the transparent resin and the tungsten oxide particles (W) later.
The morphology of the composite particles (XW 1) can be controlled by adjusting the type and content of the dispersant particles (X1) and the conditions for producing the resin molded article.
Details of the composite particle (XW 1) are described below.
< resin molded body (2) >)
The resin molded body (2) is another example of the resin molded body of the present invention.
In the resin molded article (2), the dispersant particles (X) are particulate copolymers (hereinafter referred to as "dispersant particles (X2)") containing a repeating unit derived from an alkyl (meth) acrylate (excluding methyl methacrylate) having an alkyl group having 1 to 8 carbon atoms as an ester side chain.
Further, in the resin molded body (2), the composite particles (XW) have at least one of a form in which tungsten oxide particles (W) are present on the particle surfaces of dispersant particles (X2) described later and a form in which a plurality of tungsten oxide particles (W) are contained in the particle interior of the dispersant particles (X2) (hereinafter referred to as "composite particles (XW 2)").
The resin molded body (2) can satisfy the following formulas (3) and (4) when the content W (unit: mass ppm) of the tungsten oxide particles (W) and the content X (unit: mass ppm) of the dispersant particles (X) in the resin molded body (2) are defined.
50≤w≤500 (3)
5.11w+444≤x≤10.00w+2000 (4)
In the resin molded body (2), the lower limit of the content W of the tungsten oxide particles (W) is preferably 50 mass ppm or more, from the viewpoint of improving the heat ray shielding property of the resin molded body. More preferably 60 mass ppm or more, still more preferably 100 mass ppm or more. On the other hand, the upper limit of the content W of the tungsten oxide particles (W) is preferably 500 mass ppm or less from the viewpoint that the transparency and low colorability of the resin molded article can be well maintained. More preferably 450 mass ppm or less, and still more preferably 400 mass ppm or less. The upper and lower limits mentioned above may be combined arbitrarily.
The lower limit of the content X of the dispersant particles (X2) is preferably "5.11w+444" or more from the viewpoint of improving the transparency and low coloring property of the resin molded product. More preferably "5.38w+477" or more. On the other hand, from the viewpoint of being able to maintain the transparency and low colorability of the resin molded article satisfactorily, the upper limit of the content X of the dispersant particles (X2) is preferably "10.00w+2000" or less, more preferably "7.00w+1150" or less. The upper and lower limits mentioned above may be combined arbitrarily.
Further, from the viewpoint that the balance of transparency, low coloring property and heat ray shielding property of the resin molded body becomes better, it is preferable that the above w and the above x satisfy the following formulas (5) and (6).
60≤w≤450 (5)
5.38w+477≤x≤7.00w+1150 (6)
In view of controlling the dispersion state of the tungsten oxide particles to improve the transparency, low coloring property, and heat ray shielding property of the resin molded product (2), the composite particles (XW 2) preferably have at least one of a form in which the tungsten oxide particles (W) are present on the particle surfaces of the dispersant particles (X2) and a form in which a plurality of tungsten oxide particles (W) are contained in the particles of the dispersant particles (X2).
Further, from the viewpoint of improving the transparency, low coloring property, and heat ray shielding property of the resin molded product, the composite particles (XW 2) are preferably in a form in which tungsten oxide particles (W) are substantially present on the particle surfaces of the dispersant particles (X2). The term "the form in which the tungsten oxide particles (W) are substantially present on the particle surfaces of the dispersant particles (X2)" means that the proportion of the form in which the plurality of tungsten oxide particles (W) are contained in the particle interior of the dispersant particles (X2) to the total is 10% or less.
The dispersant particles (X2) may be mixed with the transparent resin after the dispersant particles (X2) are attached to the tungsten oxide particles (W) by adsorption or the like, the transparent resin, the tungsten oxide particles (W) and the dispersant particles (X2) may be mixed at the same time, or the dispersant particles (X2) may be added to and mixed with the mixture of the transparent resin and the tungsten oxide particles (W) later.
The morphology of the composite particles (XW 2) of the present invention can be controlled by adjusting the type and content of the dispersant particles (X2) and the conditions for producing the resin molded article.
Details of the composite particles (XW 2) are described below.
The resin molded article of the present invention may further contain various additives within a range not impairing the heat ray shielding property, low coloring property, and total light transmittance in the visible light region. Specific examples of the additives include mold release agents, lubricants, plasticizers, antioxidants, antistatic agents, light stabilizers, ultraviolet absorbers, flame retardants, flame retardant aids, polymerization inhibitors, fillers, pigments, dyes, silane coupling agents, leveling agents, antifoaming agents, fluorescent agents, chain transfer agents, and the like.
The present invention can provide a resin molded article excellent in transparency, low coloring property and heat ray shielding property. More specifically, according to the present invention, a resin molded article having high total light transmittance in the visible light range and suppressed coloring can be obtained by shielding light from light sources such as fluorescent lamps and light in the infrared region included in sunlight.
(meth) acrylic acid Polymer (P)
In the present invention, the (meth) acrylic polymer (P) is preferably used as the transparent resin.
In the resin molded article of the present invention, the resin composition contains the (meth) acrylic polymer (P), so that the transparency of the resin molded article is improved, and the thermal decomposition property of the resin molded article is suppressed, whereby the thermal moldability, heat resistance and mechanical strength can be improved.
As the (meth) acrylic polymer (P) of the present invention, a homopolymer of methyl methacrylate may be used, or a copolymer containing 80 mass% or more and less than 100 mass% of a repeating unit derived from methyl methacrylate (hereinafter referred to as "MMA unit") and more than 0 mass% and 20 mass% or less of a repeating unit derived from another (meth) acrylate monomer (hereinafter referred to as "(meth) acrylate (M)") with respect to 100 mass% of the total mass of the (meth) acrylic polymer (P) may be used.
From the viewpoint of improving the heat moldability and thermal decomposition resistance of the obtained resin molded article, the (meth) acrylic polymer (P) is more preferably a copolymer containing 80 to 99 mass% of MMA units and 1 to 20 mass% of (meth) acrylate (M) units described later, and further preferably a copolymer containing 90 to 98 mass% of MMA units and 2 to 10 mass% of (meth) acrylate (M) units.
Further, from the viewpoint of improving the transparency, heat resistance and mechanical strength of the obtained resin molded article, the (meth) acrylic polymer (P) is preferably a homopolymer of MMA.
The (meth) acrylic acid ester (M) is not particularly limited as long as it is a monomer copolymerizable with methyl methacrylate. Examples of the (meth) acrylic acid ester (M) include methyl acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, t-butyl (meth) acrylate, isobutyl (meth) acrylate, n-butyl (meth) acrylate, cyclohexyl (meth) acrylate, bornyl (meth) acrylate, norbornyl (meth) acrylate, isobornyl (meth) acrylate, adamantyl (meth) acrylate, dimethyladamantanyl (meth) acrylate, methylcyclohexyl (meth) acrylate, norbornylmethyl (meth) acrylate, menthyl (meth) acrylate, pentyl (meth) acrylate, dicyclohexyl (meth) acrylate, dicyclopentenyloxyethyl (meth) acrylate, cyclodecyl (meth) acrylate, 4-t-butylcyclohexyl (meth) acrylate, and trimethylcyclohexyl (meth) acrylate. They may be used singly or in combination of two or more.
From the viewpoint of suppressing thermal decomposition and heat moldability of the resin molded product to be excellent, at least 1 monomer selected from the group consisting of ethyl acrylate, n-propyl acrylate, n-butyl acrylate and 2-ethylhexyl acrylate is preferable among the aforementioned alkyl (meth) acrylates.
The mass average molecular weight (Mw) of the (meth) acrylic polymer (P) measured by Gel Permeation Chromatography (GPC) is not particularly limited, but is preferably 150,000 to 30,000,000. By setting the lower limit of the mass average molecular weight (Mw) to 150,000 or more, the machinability and mechanical strength of the resin molded product are improved. Further, by setting the upper limit of the mass average molecular weight (Mw) to 30,000,000 or less, the heat moldability of the resin molded body is improved. The mass average molecular weight (Mw) is more preferably 160,000 to 1,000,000, still more preferably 180,000 to 700,000, particularly preferably 200,000 to 500,000.
In the production of a resin molded article made of a (meth) acrylic resin composition, the mass average molecular weight of the (meth) acrylic polymer (P) can be controlled by adjusting the type of chain transfer agent, the amount of addition, the polymerization temperature, the monomer charge composition, and the like at the time of polymerization.
< composite particle (XW) >)
The composite particles (XW) are one of the constituent components of the resin composition forming the resin molded article of the present invention.
The composite particles (XW) have at least one of a form in which the tungsten oxide particles (W) are present on the particle surfaces of the dispersant particles (X) and a form in which a plurality of tungsten oxide particles (W) are contained in the particles of the dispersant particles (X).
Further, as described above, in the resin molded body (1) which is an example of the resin molded body of the present invention, the composite particles (XW) contain the composite particles (XW 1). In addition, in the resin molded body (2) as another example, the composite particles (XW) contain the composite particles (XW 2).
When the tungsten oxide particles (W) are blended without using the dispersant particles (X), the tungsten oxide particles (W) aggregate in the resin composition forming the resin molded article, and the resin molded article tends to be colored with reduced transparency.
However, the resin molded article of the present invention contains tungsten oxide particles (W) in the form of the composite particles (XW), whereby the tungsten oxide particles (W) can be contained in a properly dispersed state without agglomerating. Therefore, the heat ray shielding property of the resin molded product is not impaired, and the transparency and low coloring property are improved.
In the present specification, the "form in which tungsten oxide particles (W) are present on the particle surfaces of dispersant particles (X)" is not particularly limited in terms of mechanisms such as adsorption and adhesion. Adsorption is preferred.
The "form in which the tungsten oxide particles (W) are present on the particle surfaces of the dispersant particles (X)" means a state in which the tungsten oxide particles (W) are weakly bound to the particle surfaces of the dispersant particles (X) by van der waals force or the like (physical adsorption), or a state in which electron exchange is performed between the adsorbed tungsten oxide particles (W) and the particle surfaces of the dispersant particles (X) to generate strong bonds (covalent bonds, ionic bonds, metal bonds, coordination bonds) between the tungsten oxide particles (W) and the particle surfaces of the dispersant particles (X) (chemical adsorption).
The method for adsorbing the particles of the dispersant particles (X) with the tungsten oxide particles (W) is not particularly limited. For example, a method in which tungsten oxide particles (W) and dispersant particles (X) are dissolved in a solvent, stirred to prepare a dispersion, and then the solvent is removed by a treatment such as vacuum drying is used.
The state of the "form in which a plurality of tungsten oxide particles (W) are contained in the particles of the dispersant particles (X)" is not particularly limited as long as the plurality of tungsten oxide particles (W) are contained, and the tungsten oxide particles (W) may be contained as primary particles or aggregated particles.
The method for containing tungsten oxide particles (W) in the particles of the dispersant particles (X) is not particularly limited. For example, a method of dispersing and mixing tungsten oxide particles (W) in a dispersant composition in advance and then forming particles as dispersant particles (X) is exemplified.
The lower limit of the dispersion particle diameter of the composite particles (XW) in the resin molded article of the present invention is preferably 100nm or more, from the viewpoint that the re-aggregation of tungsten oxide particles (W) in the resin molded article can be suppressed, the haze value of the resin molded article is reduced, and the transparency of the resin molded article is excellent. More preferably 120nm or more, still more preferably 150nm or more. The upper limit of the dispersion particle diameter of the composite particles (XW) is preferably 1000nm or less from the viewpoint of a reduction in haze value of the resin molded article and a satisfactory transparency of the resin molded article. More preferably 600nm or less, still more preferably 400nm or less. The upper limit value and the lower limit value may be arbitrarily combined.
Further alternatively, the dispersion particle diameter of the composite particles (XW) in the resin molded article is preferably 100nm to 1000 nm. More preferably from 120nm to 600nm, still more preferably from 150nm to 400 nm.
Tungsten oxide particle (W) >)
The tungsten oxide particles (W) are one of the constituent components of the resin composition forming the resin molded article of the present invention.
The resin molded body of the present invention contains tungsten oxide particles (W), whereby the heat ray shielding property of the resin molded body is improved.
As the tungsten oxide particles (W), WO is used X (2.45.ltoreq.X.ltoreq. 2.999) or M Y WO Z (0.1.ltoreq.Y.ltoreq. 0.5,2.2.ltoreq.Z.ltoreq.3.0, M being at least 1 element selected from the group consisting of Cs, rb, K, tl, in, ba, li, ca, sr, fe, sn, al and Cu), and having a hexagonal crystal structure. Examples of the composite tungsten oxide particles include Cs 0.33 WO 3 、Rb 0.33 WO 3 、K 0.33 WO 3 、Ba 0.33 WO 3 Etc. The tungsten oxide particles (W) are preferably cesium tungsten oxide particles from the viewpoint of further improving the heat ray shielding property. Acting asAs tungsten oxide particles (W), for example, YMDS-874 (trade name, manufactured by Sumitomo Metal mine Co., ltd., cs) 0.33 WO 3 ) Etc. One kind of them may be used, or two or more kinds may be used in combination.
The transparency and colorability of the resin molded body are affected by light scattering due to tungsten oxide particles (W). In order to suppress light scattering in the visible light region, the dispersion particle diameter of the tungsten oxide particles (W) is preferably 200nm or less, more preferably 100nm or less. If the dispersion particle diameter of the tungsten oxide particles (W) is sufficiently smaller than the wavelength of light, a rayleigh scattering region is formed, and the scattering strength is proportional to the 6 th power of the dispersion particle diameter, so that the transparency and low colorability of the resin molded body are further improved. Further, it is presumed that the smaller the dispersion particle diameter of the tungsten oxide particles (W), the larger the specific surface area, and therefore the heat ray shielding efficiency is improved. However, if the dispersion particle diameter is too small, particles are likely to reagglomerate with each other, and therefore the dispersion particle diameter of the tungsten oxide particles (W) is preferably 10nm or more.
< dispersant particle (X) >)
The dispersant particles (X) are one of the constituent components of the resin molded article of the present invention. The dispersant particles (X) of the present invention are dispersants in which tungsten oxide particles (W) are dispersed. The dispersant particles (X) are not necessarily spherical, and the shape is not particularly limited.
The dispersant particles (X) of the present invention have a particle shape. The dispersant particles (X) of the present invention have at least one of a form in which the tungsten oxide particles (W) are adsorbed or present on the particle surfaces thereof and a form in which the particles contain a plurality of tungsten oxide particles (W) therein. Thus, according to the study of the present inventors, etc., it was found for the first time that: the dispersant particles (X) of the present invention have an effect of inhibiting aggregation of tungsten oxide particles (W) in the resin molded article, and as a result, the obtained resin molded article has excellent transparency and low coloring.
As described above, in the resin molded article (1) which is an example of the resin molded article of the present invention, the dispersant particles (X) are dispersant particles (X1) described later.
In the resin molded body (2) as another example, the dispersant particles (X) are dispersant particles (X2) described later.
< dispersant particle (X1) >)
The dispersant particles (X1) are one of the components of the resin molded body (1) which is an example of the resin molded body of the present invention, and are a particulate copolymer (D) having a crosslinked structure (hereinafter referred to as "particulate copolymer (D)").
In the resin molded article of the present invention, tungsten oxide particles (W) are present on the surface of the particulate copolymer (D) as the dispersant particles (X1), and the composite particles (XW 1) are formed. As a result, the tungsten oxide particles (W) can be prevented from agglomerating or settling in the raw material during the production of the resin molded body. That is, primary granulation, prevention of aggregation, and prevention of sedimentation of tungsten oxide particles (W) are promoted, and dispersibility is improved. This results in a resin molded article having improved transparency, low coloring property and heat ray shielding property.
The reason for this is presumed that the particle-like copolymer (D) has a crosslinked structure and can maintain the particle shape, and therefore, tungsten oxide particles (W) present on the surface thereof can be uniformly dispersed even when mixed with the transparent resin.
The dispersion particle diameter of the particulate copolymer (D) in the resin molded body is not particularly limited. The particle diameter of the particle-like copolymer (D) dispersed in the resin molded article is preferably 100 to 1000nm.
The form of the particulate copolymer (D) of the present invention is preferably a 3-layer structure composed of the innermost polymer (a), the intermediate polymer (B) and the outer polymer (C), but is not limited thereto. In addition, the structure may be such that a further layer is provided between the innermost layer polymer (a) and the intermediate layer polymer (B). The following is presented in detail.
As a preferable form of the particulate copolymer (D), a multistage polymerized copolymer having: an outer layer polymer (C) obtained by polymerizing a monomer mixture containing at least one of an alkyl acrylate (a 1) having an alkyl group having 1 to 8 carbon atoms, which will be described later, and an alkyl methacrylate (a 2) having an alkyl group having 1 to 8 carbon atoms, which will be described later, in the presence of the rubber-like copolymer.
The outer layer polymer (C) may be a copolymer containing more than 0 mass% and 50 mass% or less of the repeating unit derived from the alkyl acrylate (a 1) and 50 mass% or more and less than 100 mass% of the repeating unit derived from the alkyl methacrylate (a 2) relative to the total mass of the outer layer polymer (C), or a homopolymer of the alkyl methacrylate (a 2).
As another embodiment of the particulate copolymer (D), a layer having a rubbery copolymer described later and a layer having the outer layer polymer (C) as the outermost layer on the outer layer side of the layer are exemplified.
The particle-like copolymer (D) has a layer having the outer layer polymer (C) at the outermost layer, thereby forming composite particles (XW 1) in which tungsten oxide particles (W) are present on the surface of the particle-like copolymer (D). As a result, the tungsten oxide particles (W) can be prevented from agglomerating or settling in the raw material during the production of the resin molded body. That is, since the dispersibility of the tungsten oxide particles (W) is improved, the transparency, low coloring property and heat ray shielding property of the resin molded body become good.
In the particulate copolymer (D) of the present invention, the form of the rubbery copolymer is not particularly limited, and examples of the rubbery copolymer include preferably a rubbery copolymer having an intermediate layer polymer (B) obtained by polymerizing a monomer mixture containing an alkyl acrylate (a 1) having an alkyl group of 1 to 8 carbon atoms, an aromatic vinyl compound (a 3) described later, and a polyfunctional monomer (a 5).
Still another preferable embodiment of the rubbery copolymer is, for example, a rubbery copolymer having an innermost polymer (a) obtained by polymerizing a monomer mixture comprising an alkyl acrylate (a 1) having an alkyl group having 1 to 8 carbon atoms, an alkyl methacrylate (a 4) having an alkyl group having 1 to 4 carbon atoms, an aromatic vinyl compound (a 3) and a polyfunctional monomer (a 5), and an intermediate polymer (B) obtained by polymerizing a monomer mixture comprising an alkyl acrylate (a 1) having an alkyl group having 1 to 8 carbon atoms, an aromatic vinyl compound (a 3) and a polyfunctional monomer (a 5) in the presence of the innermost polymer (a).
The innermost polymer (a) may be a copolymer containing 30 to 59.9 mass% of a repeating unit derived from the alkyl acrylate (a 1), 40 to 69.9 mass% of a repeating unit derived from the alkyl methacrylate (a 4), 0 to 20 mass% of a repeating unit derived from the aromatic vinyl compound (a 3), and 0.1 to 10 mass% of a structural unit derived from the polyfunctional monomer (a 5) based on the total mass of the innermost polymer (a).
The intermediate layer polymer (B) is preferably a copolymer containing 70 to 89.9 mass% of the repeating unit derived from the alkyl acrylate (a 1), 10 to 29.9 mass% of the repeating unit derived from the aromatic vinyl compound (a 3), and 0.1 to 5 mass% of the structural unit derived from the polyfunctional monomer (a 5) based on the total mass of the intermediate layer polymer (B).
The particulate copolymer (D) is preferably adjusted in refractive index to ensure good transparency, from the viewpoint of improving transparency of the resin molded article.
For example, a resin molded article of example 1 shown in fig. 1 will be described. In the resin molded article, the (meth) acrylic resin composition is composed of a (meth) acrylic resin composition containing a (meth) acrylic polymer (P) (4) and composite particles (XW 1) (3), wherein the composite particles (XW 1) (3) are composed of tungsten oxide particles (W) (1) and a particulate copolymer (D) (2).
In this example, the particulate copolymer (D) was formed with the raw material composition described in production example 1, and as a result, a resin molded article having a total light transmittance (Tt) of 60% or more, a haze (H) of 10% or less, good transparency, and a Yellow Index (YI) of less than 4.0 and suppressed coloration was obtained when the resin molded article was formed into a plate shape of about 3 mm.
The total light transmittance and haze can be measured by the methods described in the examples.
Alkyl acrylate (a 1)
The alkyl acrylate (a 1) is one of the constituent components of the outer layer polymer (C), the intermediate layer polymer (B) and the innermost layer polymer (A) of the particulate copolymer (D).
The outer layer polymer (C), the intermediate layer polymer (B) and the innermost layer polymer (A) of the particulate copolymer (D) contain a repeating unit derived from the alkyl acrylate (a 1) as one of the constituent components, whereby the transparency and low colorability of the resin molded article are improved.
As the alkyl acrylate (a 1), an alkyl acrylate having an alkyl group having 1 to 8 carbon atoms may be used. Specifically, at least 1 selected from the group consisting of methyl acrylate and ethyl acrylate, isopropyl acrylate, n-butyl acrylate, 2-ethylhexyl acrylate may be cited. These may be used singly or in combination of two or more. The alkyl acrylate (a 1) used in the intermediate layer polymer (B) is preferably n-butyl acrylate, from the viewpoint of making the tungsten oxide particles (W) present on the particle surfaces of the particulate copolymer (D) to improve the dispersibility thereof. From the viewpoint of the thermal stability of the particulate copolymer (D), the alkyl acrylate (a 1) used for the outer layer polymer (C) is preferably methyl acrylate.
Alkyl methacrylate (a 2)
The alkyl methacrylate (a 2) is one of the components of the outer polymer (C) of the particulate copolymer (D).
The outer layer polymer (C) of the particulate copolymer (D) contains a repeating unit derived from the alkyl methacrylate (a 2) as one of the constituent components, whereby the transparency and low coloring property of the resin molded article are improved.
As the alkyl methacrylate (a 2), an alkyl methacrylate having an alkyl group having 1 to 8 carbon atoms may be used. Specifically, at least 1 selected from the group consisting of methyl methacrylate, ethyl methacrylate, isopropyl methacrylate, n-butyl methacrylate, and 2-ethylhexyl methacrylate can be cited. These may be used singly or in combination of two or more. From the viewpoint of dispersibility of the particulate copolymer (D) in the (meth) acrylic resin composition, methyl methacrylate is preferable.
< aromatic vinyl Compound (a 3) >)
The aromatic vinyl compound (a 3) is one of the constituent components of the innermost polymer (a) and the intermediate polymer (B) of the particulate copolymer (D).
The intermediate layer polymer (B) of the particulate copolymer (D) contains a repeating unit derived from the aromatic vinyl compound (a 3) as one of the constituent components, whereby the transparency and low coloring property of the resin molded article are improved.
As the aromatic vinyl compound (a 3), specifically, at least 1 selected from the group consisting of styrene, α -methylstyrene, vinyl toluene is exemplified. These may be used singly or in combination of two or more. When the dispersant particles (X) are produced by emulsion polymerization or suspension polymerization, styrene is preferable from the viewpoint of high solubility of the aromatic vinyl compound (a 3) in water and easy control of polymerization.
Alkyl methacrylate (a 4)
The alkyl methacrylate (a 4) is one of the constituent components of the innermost polymer (a) of the present invention.
The innermost polymer (a) of the particulate copolymer (D) contains a repeating unit derived from the alkyl methacrylate (a 4) as one of the constituent components, whereby the transparency and low colorability of the resin molded article obtained by molding the (meth) acrylic resin composition of the present invention are improved.
As the alkyl methacrylate (a 4), an alkyl methacrylate having an alkyl group having 1 to 4 carbon atoms may be used. Specifically, at least 1 selected from the group consisting of methyl methacrylate, ethyl methacrylate, isopropyl methacrylate, and n-butyl methacrylate can be cited. These may be used singly or in combination of two or more. Among them, methyl methacrylate is preferable from the viewpoint of excellent transparency of the resin molded body.
The innermost layer polymer (a), the intermediate layer polymer (B) and the outer layer polymer (C) of the present invention may each independently further contain a structural unit derived from a polyfunctional monomer (a 5) described later or a repeating unit derived from another monofunctional monomer (a 6) described later, within a range that does not impair the performance of the obtained resin molded article.
< multifunctional monomer (a 5) >)
The polyfunctional monomer (a 5) can be used as one of the constituent components of the innermost layer polymer (a) and the intermediate layer polymer (B) of the present invention.
The polyfunctional monomer (a 5) is not particularly limited as long as it is a monomer having 2 or more copolymerizable functional groups and is a compound copolymerizable with the foregoing monomers (a 1) to (a 4) and other monofunctional monomers (a 6) described later. Examples of the polyfunctional monomer (a 5) include crosslinking agents such as ethylene glycol di (meth) acrylate, 1, 3-butylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate, allyl di (meth) acrylate, divinylbenzene, trimethylolpropane triacrylate, triallyl isocyanurate, pentaerythritol tetraacrylate, diallyl maleate, divinylbenzene, diallyl phthalate, diallyl fumarate, triallyl cyanurate, triallyl trimellitate, and the like. One kind of them may be used, or two or more kinds may be used in combination.
< other monofunctional monomer (a 6) >)
Other monofunctional monomers (a 6) may be used as one of the constituent components of the innermost layer polymer (a), the intermediate layer polymer (B) and the outer layer polymer (C) of the present invention.
The other monofunctional monomer (a 6) is not particularly limited as long as it is a monomer copolymerizable with the monomers (a 1) to (a 4) and the polyfunctional monomer (a 5). Examples of the other monofunctional monomer (a 6) include vinyl cyanide compounds such as decyl (meth) acrylate, lauryl (meth) acrylate, stearyl (meth) acrylate, and the like, alkyl (meth) acrylates having an alkyl group of 9 or more carbon atoms, (meth) acrylic acid, (meth) acrylamide, and (meth) acrylonitrile. One kind of them may be used, or two or more kinds may be used in combination.
The particulate copolymer (D) may be produced by a known method. For example, the methods described in paragraphs 0048 to 0054 of Japanese patent application laid-open No. 2006-160990 and the methods described in paragraphs 0030 to 0036 of International publication No. 2005/097856 can be used.
< dispersant particle (X2) >)
The dispersant particles (X2) are one of the constituent components of a resin molded body (2) which is another example of the resin molded body of the present invention.
The resin molded article of the present invention contains the dispersant particles (X2) to improve the dispersibility of the tungsten oxide particles (W). This promotes primary granulation, aggregation and sedimentation prevention of the tungsten oxide particles (W), and further improves the heat ray shielding property and transparency of the resin molded article.
As the dispersant particles (X2) of the present invention, a particulate polymer containing a repeating unit (hereinafter referred to as "alkyl (meth) acrylate unit") derived from an alkyl (meth) acrylate having an alkyl group having 1 to 8 carbon atoms as an ester side chain (excluding methyl methacrylate) is used from the viewpoint of being capable of improving the dispersibility of the tungsten oxide particles (W) and improving the transparency and heat ray shielding properties of the resin molded product. The content of the alkyl (meth) acrylate unit in the polymer is preferably 35 mass% or more and 75 mass% or less relative to the total mass of the polymer, from the viewpoint of improving transparency and heat ray shielding property of the resin molded product.
Examples of the alkyl methacrylate having an alkyl group having 1 to 8 carbon atoms as an ester side chain include ethyl methacrylate, isopropyl methacrylate, n-butyl methacrylate, 2-ethylhexyl methacrylate, and the like. These may be used singly or in combination of two or more. Examples of the alkyl acrylate having an alkyl group having 1 to 8 carbon atoms as an ester side chain include methyl acrylate, ethyl acrylate, isopropyl acrylate, n-butyl acrylate, 2-ethylhexyl acrylate, and the like. These may be used singly or in combination of two or more. N-butyl acrylate is preferably used.
Further, from the viewpoint of improving the transparency of the obtained resin molded product, the copolymer constituting the dispersant particle (X2) may contain MMA units. From the viewpoint of better transparency of the resin molded body, the content of the MMA unit of the polymer constituting the dispersant particle (X2) is preferably 25 mass% or more and 65 mass% or less with respect to the total mass.
Specific examples of the copolymer include a copolymer containing a butyl acrylate unit, a butyl methacrylate unit and a methyl methacrylate unit, a copolymer containing an ethyl acrylate unit, an ethyl methacrylate unit and a methyl methacrylate unit, and the like.
Further, in the present invention, the preferable embodiment of the dispersant particle (X2) is the copolymer (X2-a) described below, from the viewpoint that the dispersibility of the tungsten oxide particles (W) can be improved and the transparency and heat ray shielding properties of the resin molded product can be improved.
< copolymer (X2-A) >)
The copolymer (X2-A) can be used as one of the embodiments of the polymer constituting the above-mentioned dispersant particle (X2).
The resin molded article of the present invention contains the copolymer (X2-a) as the dispersant particles (X2), and thus can be excellent in transparency and low coloring property without impairing the heat ray shielding property of the resin molded article.
The copolymer (X2-a) is a copolymer containing at least one of a repeating unit derived from an alkyl acrylate (a 7) having an alkyl group having 2 to 8 carbon atoms as an ester side chain (hereinafter referred to as "alkyl acrylate (a 7) unit") and a repeating unit derived from an alkyl methacrylate (a 8) having an alkyl group having 2 to 8 carbon atoms as an ester side chain (hereinafter referred to as "alkyl methacrylate (a 8) unit").
The copolymer (X2-a) contains an alkyl acrylate (a 7) unit, and is preferable in terms of suppressing thermal decomposition of the resin molded product and improving the heat moldability. Further, the dispersibility of the tungsten oxide particles (W) becomes good, and the transparency, low coloring property and heat ray shielding property of the resin molded body are improved.
The copolymer (X2-A) contains the alkyl methacrylate (a 8) unit, whereby the dispersibility of the dispersant particles (X) is improved. As a result, the dispersibility of the tungsten oxide particles (W) becomes good, and the transparency, low coloring property, and heat ray shielding property of the resin molded body are improved.
The lower limit of the content of the alkyl acrylate (a 7) unit in the copolymer (X2-a) is not particularly limited, but is preferably 5 mass% or more with respect to the total mass of the copolymer (X2-a) from the viewpoint that the transparency of the resin molded article becomes good. More preferably 25% by mass or more, and still more preferably 30% by mass or more. On the other hand, the upper limit of the content of the alkyl acrylate (a 7) unit is not particularly limited, but is preferably 65 mass% or less with respect to the total mass of the copolymer (X2-a) from the viewpoint of improving the transparency of the resin molded product. More preferably 40 mass% or less, and still more preferably 35 mass% or less. The upper limit value and the lower limit value may be arbitrarily combined.
The lower limit of the content of the alkyl methacrylate (a 8) unit in the copolymer (X2-a) is not particularly limited, but is preferably 10 mass% or more with respect to the total mass of the copolymer (X2-a) from the viewpoint that the transparency of the resin molded article becomes good. More preferably 15% by mass or more, and still more preferably 20% by mass or more. On the other hand, the upper limit of the content of the alkyl methacrylate (a 8) unit is not particularly limited, but is preferably 30 mass% or less with respect to the total mass of the copolymer (X2-a) from the viewpoint of improving the transparency of the resin molded product. More preferably 25 mass% or less, and still more preferably 20 mass% or less. The upper limit value and the lower limit value may be arbitrarily combined.
Further alternatively, the copolymer (X2-A) preferably contains 5 to 65 mass% of the alkyl acrylate (a 7) unit and 10 to 30 mass% of the alkyl methacrylate (a 8) unit, based on the total mass of the copolymer (X2-A).
Further, the copolymer (X2-A) may contain MMA units from the viewpoint of improving the transparency of the resin molded body. The lower limit of the content of the MMA unit in the polymer is not particularly limited, and may be 25 mass% or more with respect to the total mass of the copolymer (X2-A) from the viewpoint of improving the transparency of the resin molded product. On the other hand, the upper limit of the content of MMA units is not particularly limited, and may be 65 mass% or less with respect to the total mass of the copolymer (X2-A) from the viewpoint of improving the transparency of the resin molded product. The upper limit value and the lower limit value may be arbitrarily combined.
In the case where MMA units are contained in one embodiment of the copolymer (X2-A), there is a copolymer containing 5 to 65 mass% of alkyl acrylate (a 7) units, 10 to 30 mass% of alkyl methacrylate (a 8) units, and 25 to 65 mass% of MMA units, based on the total mass of the copolymer (X2-A). More preferably, the copolymer contains 20 to 40 mass% of an alkyl acrylate (a 7) unit, 10 to 30 mass% of an alkyl methacrylate (a 8) unit, and 40 to 60 mass% of an MMA unit.
Examples of the alkyl acrylate (a 7) include ethyl acrylate, n-propyl acrylate, isopropyl acrylate, t-butyl acrylate, isobutyl acrylate, n-butyl acrylate, cyclohexyl acrylate, and 2-ethylhexyl acrylate. They may be used singly or in combination of two or more. The alkyl acrylate is preferably at least 1 monomer selected from the group consisting of n-butyl acrylate, n-ethyl acrylate, n-propyl acrylate and 2-ethylhexyl acrylate, from the viewpoint that the dispersibility of the tungsten oxide particles (W) becomes good and the transparency of the resin molded product obtained by the reduction of the refractive index difference from the (meth) acrylic polymer (P) is improved.
Specific examples of the alkyl methacrylate (a 8) include ethyl methacrylate, n-propyl methacrylate, isopropyl methacrylate, t-butyl methacrylate, isobutyl methacrylate, n-butyl methacrylate, and cyclohexyl methacrylate. They may be used singly or in combination of two or more. The alkyl methacrylate is preferably at least 1 monomer selected from the group consisting of n-butyl methacrylate and isobutyl methacrylate, from among the aforementioned alkyl methacrylates, since the dispersibility of the tungsten oxide particles (W) is improved and the transparency of the resin molded body is improved by the decrease in the refractive index difference from the (meth) acrylic polymer (P).
As the copolymer (X2-A), specifically, a copolymer containing 25 to 65% by mass of MMA unit, 10 to 30% by mass of n-Butyl Methacrylate (BMA) unit and 5 to 65% by mass of n-Butyl Acrylate (BA) unit can be cited.
The copolymer (X2-A) may contain repeating units derived from the other monomer (a 9) within a range not to impair the performance of the resin molded body.
The other monomer (a 9) is not particularly limited as long as it is the monomer copolymerizable with the alkyl acrylate (a 7), the alkyl methacrylate (a 8) and methyl methacrylate. Examples of the other monomer (a 9) include: an aromatic vinyl monomer such as dodecyl (meth) acrylate, tridecyl (meth) acrylate, stearyl (meth) acrylate, isobornyl (meth) acrylate, acrylic acid, tetrahydrofurfuryl (meth) acrylate, norbornyl (meth) acrylate, adamantyl (meth) acrylate, dicyclopentenyl (meth) acrylate, dicyclopentanyl (meth) acrylate, tetracyclododecyl (meth) acrylate, cyclohexanedimethanol mono (meth) acrylate, etc., each having an alkyl group having 9 or more carbon atoms as an ester side chain, styrene, and α -methylstyrene. They may be used singly or in combination of two or more.
Method for producing resin molded article
The method for obtaining the resin molded article of the present invention includes a method of polymerizing a polymerizable composition (M2) described later.
Examples of the radical polymerization initiator used for polymerizing the polymerizable composition (M2) to obtain a resin molded article include known azo compounds such as 2,2 '-azobis (isobutyronitrile) and 2,2' -azobis (2, 4-dimethylvaleronitrile), and known organic peroxides such as benzoyl peroxide and lauroyl peroxide. They may be used singly or in combination of two or more. If necessary, a known polymerization accelerator such as an amine or a thiol may be used in combination with the radical polymerization initiator.
The content of the radical polymerization initiator in the polymerizable composition (M2) is not particularly limited, and can be appropriately determined by a person skilled in the art according to known techniques. The amount of the polymerizable composition (M2) is usually 0.01 to 0.5 parts by mass based on 100 parts by mass of the total mass of the composition.
The polymerization temperature at the time of polymerizing the polymerizable composition (M2) is not particularly limited, and can be appropriately determined by a person skilled in the art according to known techniques. Generally, the temperature is appropriately set in the range of 20 to 150℃depending on the kind of radical polymerization initiator used. The polymerizable composition (M2) may be polymerized under multistage temperature conditions as needed.
Examples of the polymerization method of the polymerizable composition (M2) include bulk polymerization, suspension polymerization, emulsion polymerization and dispersion polymerization. Among them, the bulk polymerization method is preferable in terms of productivity, and among them, the cast polymerization (cast polymerization) method is more preferable.
As the casting polymerization method, for example, in the case of obtaining a resin molded body having a plate-like morphology, the following cell casting (cell cast) method is exemplified: a space formed by facing 2 glass plates or metal plates (SUS plates) and a gasket such as a soft resin tube disposed at the edge portion thereof is used as a mold, a slurry obtained by polymerizing the polymerizable composition (M2) or a part of the polymerizable composition (M2) is injected into the mold, and the polymerization is completed by performing a heating-polymerization treatment, and the resin molded body is taken out of the mold. Alternatively, the following continuous casting method may be used: a space formed by 2 stainless steel endless belts and gaskets such as soft resin pipes arranged on both side edges of the endless belts, which are relatively operated at a predetermined interval in the same direction, is used as a mold, a slurry obtained by polymerizing a polymerizable composition (M2) or a part of the polymerizable composition (M2) is continuously injected into the mold from one end of the endless belts, and a heat-polymerization treatment is performed to complete the polymerization, and a resin molded body is continuously taken out from the other end of the endless belts.
The interval between the mold voids can be appropriately adjusted by the thickness (diameter) of the gasket, and a resin molded article having a desired thickness can be obtained. The thickness of the resin molded body is usually set to a range of 0.1 to 50 mm.
Polymerizable composition (M2)
The polymerizable composition (M2) is one embodiment of a raw material for obtaining the resin molded article of the present invention, and is a composition containing a raw material composition (M1), tungsten oxide particles (W), dispersant particles (X), and a known radical polymerization initiator, which will be described later.
In the resin molded article (1) which is an example of the resin molded article of the present invention, the polymerizable composition (M2) is a composition containing a raw material composition (M1) described later, tungsten oxide particles (W), the dispersant particles (X1), and a known radical polymerization initiator.
In the production of the resin molded article (1), the content W of the tungsten oxide particles (W) contained in the polymerizable composition (M2) M2 The unit (unit: mass ppm) is not particularly limited, and may be in the range of 4 mass ppm to 13000 mass ppm relative to the total mass of the polymerizable composition (M2).
Content X of the dispersant particle (X1) contained in the polymerizable composition (M2) M2 (unit: mass ppm) is not particularly limited, and may be in the range of 50 mass ppm to 20000 mass ppm.
In the resin molded article (2) as another example, the polymerizable composition (M2) is a composition containing a raw material composition (M1) described later, tungsten oxide particles (W), the dispersant particles (X2), and a radical polymerization initiator. The radical polymerization initiator is not particularly limited.
In the production of the resin molded body (2), the content W of tungsten oxide particles (W) contained in the polymerizable composition (M2) M2 (unit: mass ppm) and the content X of the dispersant particles (X2) M2 (unit: mass ppm) may be set to the range of the following formulas (7) and (8).
50≤w M2 ≤500 (7)
5.11w M2 +444≤x M2 ≤10.00w M2 +2000 (8)
The dispersant particles (X2) may be directly added to the raw material composition (M1), or particles obtained by melt-kneading or mixing the dispersant particles (X2) with an appropriate (meth) acrylic resin may be added to the raw material composition (M1).
Raw material composition (M1) >)
The raw material composition (M1) is a constituent component of the polymerizable composition (M2) and is also a raw material component of the (meth) acrylic polymer (P).
The raw material composition (M1) is a monomer composition containing MMA, specifically, a monomer composition containing MMA and (meth) acrylic acid ester (M), or a composition composed of MMA alone. As the (meth) acrylic acid ester (M), the same monomers as those described in the column of the (meth) acrylic acid polymer (P), (meth) acrylic acid ester (M) "can be used.
When the raw material composition (M1) contains the (meth) acrylate (M), the heat moldability and thermal decomposition resistance of the resin molded product are improved.
By containing MMA in the raw material composition (M1), the transparency, heat resistance and mechanical strength of the resin molded product can be further improved.
The content of MMA and (meth) acrylate (M) in the raw material composition (M1) is not particularly limited, and may be appropriately set so that, for example, the total mass of the (meth) acrylic polymer (P) in the finally obtained (meth) acrylic polymer (P) is 100 mass%, the MMA unit is 60 mass% or more and 100 mass% or less, and the (meth) acrylate (M) unit is 0 mass% or more and 40 mass% or less.
In addition, the raw material composition (M1) may contain a polymer containing MMA units in advance. Specifically, the raw material composition (M1) may contain a polymer (a) described later in advance. Since the raw material composition (M1) contains the polymer (a) and the polymerizable composition (M2) forms a viscous liquid (hereinafter referred to as "slurry"), the polymerization time can be shortened and the productivity can be improved.
Examples of the method for obtaining the slurry include a method of dissolving the polymer in the raw material composition (M1) and a method of adding a known radical polymerization initiator to the raw material composition (M1) and partially polymerizing the mixture.
In one embodiment of the polymerizable composition (M2), when the polymerizable composition (M2) is a slurry, a composition containing the following polymer (a) and monomer composition (M) is exemplified.
Polymer (a): a polymer containing 60 mass% or more and less than 100 mass% of MMA units and more than 0 mass% and 40 mass% or less of the aforementioned (meth) acrylate (M) units, or a polymer composed of 100 mass% of MMA units, relative to the total mass of the polymer (a).
Monomer composition (m): a monomer composition containing 60 mass% or more and less than 100 mass% of MMA, more than 0 mass% and 40 mass% or less of (meth) acrylic acid ester (M), or a monomer composition composed solely of MMA, relative to the total mass of the monomer composition (M).
< resin molded article >)
When the resin molded article of the present invention is composed of the (meth) acrylic resin composition, the transparency, low coloring property and heat ray shielding property are more excellent.
When the resin molded article of the present invention is composed of the (meth) acrylic resin composition, the following conditions can be satisfied: the total light transmittance of 3mm in the optical path length of transmitted light measured in accordance with JIS K7361-1 in the wavelength range of 380 to 780nm is 60% or more, the haze of 3mm in the optical path length of transmitted light measured in accordance with JIS K7136 is 10% or less, the Yellow Index (YI) of 3mm in the optical path length of transmitted light measured in accordance with ASTM D1925 is less than 4.0, and the heat ray blocking rate of 3mm in the optical path length of transmitted light measured in the wavelength range of 780 to 2100nm is 40% or more, measured in accordance with the method described later.
The total light transmittance when the optical path length of the transmitted light is 3mm is 60% or more, and the value when the total light transmittance is measured by setting the optical path length of the transmitted light to 3mm is defined, instead of limiting the thickness of the resin molded body to 3 mm.
The haze of the resin molded article is 10% or less when the optical path length of the transmitted light is 3mm, and the haze is measured by defining the optical path length of the transmitted light to be 3mm, instead of limiting the thickness of the resin molded article to 3 mm.
The YI of the transmitted light having an optical path length of 3mm is lower than 4.0, and the value of YI measured by setting the optical path length of the transmitted light to 3mm is not limited to 3mm in thickness of the resin molded body.
The heat ray blocking rate of 40% or more when the optical path length of the transmitted light is 3mm is defined as a value when the heat ray blocking rate is measured with the optical path length of the transmitted light being 3mm, not with the thickness of the resin molded body being 3 mm.
This can improve the transparency, low coloring property, and heat ray shielding property of the resin molded product.
The lower limit of the total light transmittance is 60% or more from the viewpoint of excellent transparency of the resin molded product. More preferably 70% or more. On the other hand, the upper limit of the total light transmittance is not particularly limited, but is set to 90% or less, preferably 85% or less, from the viewpoint of maintaining good heat ray shielding property.
The upper limit of haze is 10% or less from the viewpoint of excellent transparency of the resin molded body. More preferably 8% or less, and still more preferably 5% or less. The lower limit of the haze is not particularly limited, and is usually set to 0.2% or more from the viewpoint of being able to maintain the heat ray shielding property satisfactorily.
The upper limit of YI is less than 4.0 from the viewpoint of excellent low coloring property of the resin molded body. More preferably less than 1.0, and still more preferably less than 0.5. On the other hand, the lower limit of YI is not particularly limited, and the smaller the value, the more preferable. However, if the YI value is too small, the color may be undesirably blue, and is usually set to-4.0 or more, more preferably to-3.0 or more, and still more preferably to-2.0 or more.
The lower limit of the heat ray blocking rate is 40% or more. More preferably 55% or more, still more preferably 60% or more. On the other hand, the upper limit of the heat ray blocking rate is not particularly limited, and may be set to 100%.
The resin molded article having a total light transmittance of 60% or more, a haze of 10% or less, a YI of less than 4.0, and a heat ray blocking rate of 40% or more is a resin molded article formed from a (meth) acrylic resin composition containing a (meth) acrylic polymer (P), tungsten oxide particles (W), and dispersant particles (X), and is a resin molded article formed from a (meth) acrylic resin composition containing composite particles (XW) having at least one of a form in which tungsten oxide particles (W) are present on the particle surfaces of the dispersant particles (X) and a form in which a plurality of tungsten oxide particles (W) are contained in the particles of the dispersant particles (X). In the resin molded article, the tungsten oxide particles (W) are preferably contained in an amount of 0.05g/m per unit area of the projected area of the resin molded article 2 Above 3.00g/m 2 The following is given.
The resin molded article of the present invention has high transparency in the visible light range and is suppressed in coloration because of excellent transparency, low coloration, and heat ray shielding properties. Therefore, the coating composition is suitable for applications requiring a transparent protective material for lighting devices, billboards and the like with low presence feeling, particularly ceiling materials and window materials for buildings, automobiles, trains, buses and the like. In addition, excellent transparency can be exhibited, and various colors can be adjusted by adding pigments and dyes.
Examples
The present invention will be described below with reference to examples. Hereinafter, "parts" and "%" represent "parts by mass" and "% by mass", respectively. In addition, the compounds used in examples and comparative examples are abbreviated as follows.
MMA: methyl methacrylate
MAA: methacrylic acid
ST: styrene
BA: acrylic acid n-butyl ester
BMA: n-butyl methacrylate
MA: acrylic acid methyl ester
1,3BDDM: 1, 3-butylene dimethacrylate, 1, 3-dimethylglyoxylic acid, which is used for the very long period of time
BDMA: 1, 3-butanediol dimethacrylate (1, 3-dimethylglyoxylic acid) コ sheath
AMA: allyl methacrylate
SFS: sodium formaldehyde sulfoxylate
HPP: tert-hexyl peroxypivalate (manufactured by Nipple Co., ltd.)
BHP: tert-butyl hydroperoxide (Tokyo chemical industry Co., ltd.)
CHP: cumene hydroperoxide (Tokyo chemical industry Co., ltd.)
DBP: di-tert-butyl peroxide (manufactured by Tokyo chemical industry Co., ltd.)
OcSH: n-octyl mercaptan
AVN:2, 2-azobis (2, 4-dimethylvaleronitrile) (trade name, fuji film and manufactured by Wako pure chemical industries, ltd.)
W oxide particles (W-1): a dispersion powder containing tungsten oxide particles (trade name: YMDS-874, manufactured by Sumitomo Metal mine Co., ltd.) containing 23.0% by mass of tungsten oxide particles
Particulate copolymer (D-1): dispersant particles produced in production example 1
Particulate copolymer (D-2): dispersant particles produced in production example 2
Copolymer (D-3): crosslinked acrylic acid based fine particles (trade name: MA1002, manufactured by Japanese catalyst Co., ltd.)
Copolymer (D-4): commercially available acrylic copolymer (copolymer comprising MMA unit, EA unit and MAA unit, mass average molecular weight of 35,000)
Copolymer (D-5): commercially available acrylic copolymer (copolymer comprising MMA unit, EA unit and MAA unit, mass average molecular weight of 55,000)
Dispersant copolymer (X-1): dispersant particles produced in production example 3
Dispersant copolymer (X-2): polyester resin (trade name: BYK-W9010, manufactured by Pick chemical Japan Co., ltd.)
Emulsifier (1): mono-n-dodecyloxy tetraoxyethylene sodium phosphate
Emulsifying agent (2): sodium hydroxide partial neutralization of a mixture of 40% mono (polyoxyethylene nonylphenyl ether) phosphoric acid and 60% di (polyoxyethylene nonylphenyl ether) phosphoric acid
< evaluation method >)
The evaluations in examples and comparative examples were carried out by the following methods.
(1) Total light transmittance (Tt)
As an index of transparency, an integrating sphere type light transmittance measuring device (model name: NDH4000, manufactured by Nippon electric color industry Co., ltd.) was used, and a test piece (50 mm long. Times. 50mm wide, thickness: 3 mm) of a resin molded article was subjected to incidence of parallel light in accordance with JIS K7361-1, to measure total light transmittance (ratio of total transmitted light beam to balanced incident light beam) in a wavelength range of 380 to 780 nm. Using 3 test pieces, 1 measurement was performed for each test piece, and the average value thereof was taken as the total light transmittance (Tt).
(2) Haze (H)
As an index of transparency, an integrating sphere type light transmittance measuring device (model name: NDH4000, manufactured by Nippon electric color industry Co., ltd.) was used, and a test piece (50 mm long. Times. 50mm wide, thickness: 3 mm) of a resin molded article was subjected to incidence of parallel light in accordance with JIS K7136 to measure haze (%) in a wavelength range of 380 to 780nm (proportion of diffuse transmission light beam to balanced incidence light beam). Using 3 test pieces, 1 measurement was performed for each test piece, and the average value thereof was taken as a haze value.
(3) Determination of transparency
Based on the measured values of the total light transmittance (Tt) and the haze (H), the transparency was evaluated at three levels according to the following determination criteria.
(determination criterion)
AA: the total light transmittance (Tt) is 70% or more and the haze (H) is 10% or less.
A: the total light transmittance (Tt) is 60% or more and less than 70%, and the haze (H) is 10% or less.
B: does not conform to AA, A.
(4) Yellow Index (YI)
As an index of low coloring property, a Yellow Index (YI) of a test piece (50 mm long by 50mm wide by 3mm thick) of the resin molded article was measured using a spectroscopic color difference meter (model name: SE-7700, manufactured by Nippon electric color industry Co., ltd.) in accordance with ASTM D1925 using a C light source. Using 3 test pieces, 1 measurement was performed for each test piece, and the average value thereof was taken as Yellow Index (YI). Further, three levels of evaluation were performed according to the following determination criteria.
(determination criterion)
AA: YI is lower than 1.0.
A: YI is 1.0 or more and less than 4.0.
B: YI is 4.0 or more.
(5) Heat ray blocking rate
As an index of the heat ray shielding property, the heat ray shielding rate in the wavelength range of 780 to 2100nm was measured as follows. A test piece (50 mm long by 50mm wide, 3mm thick) of the resin molded article was subjected to measurement of spectral transmittance (unit:%) at a wavelength of 780 to 2100nm using an ultraviolet-visible near-infrared spectrophotometer (model name: UH4150, manufactured by Hitachi-high technology). Next, according to the following formula (9), the obtained spectral transmittance is multiplied by a weight coefficient indicating a standard spectral distribution of solar radiation specified in JIS R3106, and the weighted average is performed to obtain a heat ray transmittance τ e (unit:%).
[ number 1]
Figure GDA0002920607130000351
In the formula (9), E (lambda) is a weight coefficient at the wavelength lambda, and τ (lambda) is a spectral transmittance (unit:%) at the wavelength lambda. ]
Next, the heat ray blocking rate (unit:%) at a wavelength of 780 to 2100nm was calculated by the following formula (10).
[ number 2]
[ Heat ray Barrier Rate (%) =100- [ Heat ray transmittance τ ] e (％)](10)
Further, the quasi-heat ray blocking rate was evaluated at four levels according to the following determination criteria.
(determination criterion)
S: the heat ray blocking rate is more than 90%.
AA: the heat ray blocking rate is 55% or more and less than 90%.
A: the heat ray blocking rate is 40% to 55%.
B: the heat ray blocking rate was less than 40%.
(6) Dispersed particle diameter of composite particle (XW)
The test piece of the resin molded body was cut in a direction perpendicular to the principal plane. A sample for a transmission electron microscope was cut out from the cut surface using an ultra-thin microtome (manufactured by Leka microscope Co., ltd., model name: EM-ULTRACUTUCT). The sample was observed with a transmission electron microscope (model name: JEM-1011, manufactured by Japanese electronic industries, ltd.) at a magnification of 5 ten thousand times to obtain a TEM observation image.
When composite particles (XW) in which tungsten oxide particles (W) are adsorbed on particles of the dispersant particles (X) are observed, the maximum diameter of the particles observed on a TEM observation image is measured for any 20 composite particles (XW), and the average value thereof is taken as the dispersed particle diameter of the composite particles (XW).
(7) Mass average molecular weight (Mw)
The mass average molecular weight (Mw) of the (meth) acrylic polymer (P) was measured by Gel Permeation Chromatography (GPC). 20mg of (meth) acrylic polymer (P) was dissolved in 10ml of THF, and the mixture was allowed to stand still at 40℃for one night. To this was added W400 (2-2' -methylenebis (4-methyl-6-t-butylphenol)) as an internal standard, and the solution obtained by filtration with a 0.2 μm filter was used as a sample for GPC measurement. In GPC measurement, 2 separation columns (trade name: SUPER HM-H, manufactured by Tosoh Co., ltd.) were used in series in a high performance liquid chromatography measurement apparatus (model name: HLC-8320, manufactured by Tosoh Co., ltd.). In addition, the detector uses a differential refractometer. The measurement was performed under conditions of a column temperature of 40 ℃, a flow rate of the mobile phase of THF, a flow rate of the mobile phase of 0.6ml/min, and a sample injection amount of 10. Mu.l. The molecular weight in terms of a standard polymer was determined using several kinds of polystyrene (Mw: 340 ～ 1,950,000) having known molecular weights as the standard polymer.
Production example 1 production of the particulate copolymer (D-1):
the following components were put into a 5-neck flask equipped with a stirrer, a reflux condenser, a nitrogen gas inlet, a monomer addition port, and a thermometer. ( Numerals in parentheses indicate parts by mass. The following description is made in the same manner. )
Deionized water (300 parts)
SFS (0.48 parts)
Ferrous sulfate (0.4X10) -6 Parts by weight of
Ethylene diamine tetraacetic acid disodium salt (1.2X10) -6 Parts by weight of
Next, the temperature was raised to 80℃while the system was purged with nitrogen, and a mixture (e-1) having the following composition was charged for 2 hours, and the mixture was kept at 80℃for 1 hour to complete polymerization, thereby obtaining latex (L-1).
The polymerization rate of the obtained latex (L-1) was 99% or more.
< mixture (e-1) >)
MMA (22 parts)
ST (2.0 parts)
BA (16 parts)
1,3BDDM (1.0 parts)
AMA (0.1 part)
BHP (0.04 parts)
Emulsifier (1) (1.3 parts)
Next, to the obtained latex (L-1), a mixture (e-2) having the following composition was added, and after holding at 80℃for 15 minutes, a mixture (e-3) having the following composition was added dropwise over 3 hours, and after holding at 80℃for 3 hours, polymerization was completed to obtain latex (L-2).
The polymerization rate of the obtained latex (L-2) was 99% or more.
< mixture (e-2) >)
SFS (0.2 parts)
Deionized water (5.0 parts)
< mixture (e-3) >)
ST (10 parts)
BA (50 parts)
1,3BDDM (0.2 parts)
AMA (1.2 parts)
CHP (0.2 parts)
Emulsifier (1) (2.5 parts)
Next, to the obtained latex (L-2), a mixture (e-4) having the following composition was added, and after holding at 80℃for 15 minutes, a mixture (e-5) having the following composition was added dropwise over 2 hours, and after holding at 80℃for 1 hour, polymerization was completed to obtain a latex (L-3).
The final latex (L-3) obtained had a polymerization rate of 99% or more.
< mixture (e-4) >
SFS (0.2 parts)
Deionized water (5.0 parts)
< mixture (e-5) >)
MMA (57.0 parts)
MA (3.0 parts)
BHP (0.1 part)
OcSH (0.2 parts)
300 parts of a 1.6% aqueous solution of calcium acetate as a coagulant was charged into a stainless steel vessel, the temperature was raised to 90℃with stirring, 300 parts of the resulting final latex (L-3) was continuously added over 10 minutes to coagulate, and the mixture was then kept for 5 minutes. Then cooled to room temperature, washed with deionized water, and centrifuged at 1300G for 3 minutes, and filtered to give a wet polymer.
The wet polymer was dried at 75℃for 48 hours to give a white powdery polymer. This was used as the particulate copolymer (D-1).
Production example 2 production of the particulate copolymer (D-2):
the following components were put into a 5-neck flask equipped with a stirrer, a reflux condenser, a nitrogen gas inlet, a monomer addition port, and a thermometer.
Deionized water (300 parts)
Sodium carbonate (0.09 parts)
Boric acid (0.9 part)
Next, 3.8 parts of the mixture (e-6) having the following composition was added to the system while raising the temperature to 80℃with nitrogen substitution, and the mixture was kept for 15 minutes, and then the remaining mixture (e-6) was continuously added at a rate of 5.1 parts/hour, and the mixture was kept for 1 hour, whereby polymerization of the innermost layer was carried out.
< mixture (e-6) >
ST (10 parts)
BA (50 parts)
BDMA (0.2 parts)
AMA (1.2 parts)
CHP (0.2 parts)
Emulsifier (2) (2.0 parts)
Next, 5.2 parts of the mixture (e-7) of the following composition was added, and after holding for 15 minutes, 60.6 parts of the mixture (e-8) of the following composition was continuously added at a rate of 0.61 parts/hour, and then held for 1 hour, and polymerization of the outermost layer was carried out to obtain latex (L-4).
< mixture (e-7) >)
SFS (0.2 parts)
Deionized water (5 parts)
< mixture (e-8) >
MMA (57.0 parts)
BA (3.0 parts)
DBP (0.1 part)
OcSH (0.2 parts)
Then, this latex (L-4) was coagulated, washed, dehydrated and dried under the same conditions as in production example 1 to obtain a white powdery polymer. This was used as the particulate copolymer (D-2).
Production example 3 production of dispersant copolymer (X-1):
a mixture of 260 parts of ion-exchanged water, 1.5 parts of dioctyl sodium sulfosuccinate, 0.2 part of potassium persulfate, 30 parts of MMA and 0.05 part of OcSH was charged into a reaction vessel equipped with a stirrer and a reflux condenser, and the inside of the vessel was replaced with nitrogen, and then the reaction vessel was heated to 65℃with stirring and stirred for 2 hours with heating.
Then, a mixture of 20 parts of BMA, 30 parts of BA and 0.5 part of OcSH was added to the reaction system over 1 hour, and after the addition was completed, the mixture was further stirred for 2 hours.
Then, a mixture of 20 parts of MMA and 0.05 part of OcSH was added to the reaction system over 30 minutes, and after further stirring for 2 hours with heating, the polymerization reaction was terminated, and cooled to obtain a latex.
Adding the obtained latex into aluminum chloride aqueous solution for salting out and coagulation, and then washing and drying the obtained coagulum to obtain the polymerAnd (3) a compound. This was used as the dispersant copolymer (X-1) and as dispersant particles. The glass transition temperature of the dispersant copolymer (X-1) was 23 ℃. In addition, use is made of 1 As a result of the well-known composition analysis method by the H-NMR method, the dispersant copolymer (X-1) was a copolymer containing 50% by mass of MMA units, 20% by mass of BMA units and 30% by mass of BA units.
Example 1
(1) Slurry manufacture
100 parts by mass of MMA was supplied to a reactor (polymerizer) equipped with a cooling tube, a thermometer and a stirrer, stirred for 15 minutes while bubbling with nitrogen, and then heated to a temperature of 60℃while stirring. Next, 0.1 part by mass of AVN as a radical polymerization initiator was added, and the above-mentioned monomer composition was further heated to 100℃with stirring, and then kept for 13 minutes. Then, the mixture was cooled to room temperature to obtain slurry (Z). The content of the polymer (a) in the slurry (Z) was 20% by mass.
(2) Cast polymerization
To 92 parts by mass of the slurry (Z) were added 8 parts by mass of MMA, 0.3 part by mass of the particulate copolymer (D-1) produced in production example 1, and 0.06 part by mass (containing 13.8X10) -3 Tungsten oxide particles) as tungsten oxide particles (W-1) and 0.4 parts by mass of HPP as a polymerization initiator, and the resultant was dissolved as a polymerizable composition (M2).
A soft resin spacer was provided at the end of 2 SUS plates disposed to face each other so that the gap interval between the 2 SUS plates was 4.1mm, and a mold was produced. Next, the polymerizable composition (M2) was flowed into the mold, sealed with a soft resin gasket, heated to 80 ℃, held for 40 minutes, then heated to 130 ℃ and held for 30 minutes, and polymerized. Then, the mixture was cooled to room temperature, and the SUS plate was removed to obtain a plate-like resin molded body having a thickness of 3 mm. The evaluation results of the obtained resin molded bodies are shown in table 1, and photographs taken with a TEM are shown in fig. 1. In the table, (P), (W) and (X) are calculated from the amounts of the polymerizable composition to be charged, respectively, relative to the resin molded article.
Further, the mass average molecular weight (Mw) of the (meth) acrylic polymer (P) in the resin molded body was 350,000.
Comparative example 1
A resin molded article was obtained in the same manner as in example 1, except that the dispersant particles (X) were not used. The evaluation results of the resin molded bodies are shown in table 1, and photographs taken with a TEM are shown in fig. 2.
TABLE 1
Figure GDA0002920607130000401
*1 content ratio relative to the total mass of the (meth) acrylic polymer (P)
Examples 2 to 15
A resin molded article was obtained in the same manner as in example 1, except that the kind and the blending amount of the tungsten oxide particles (W) and the dispersant particles (X) were changed as described in table 2. The evaluation results of the resin molded bodies are shown in table 2.
TABLE 2
Figure GDA0002920607130000411
Comparative examples 2 to 7
A resin molded article was obtained in the same manner as in example 1, except that the kind and the blending amount of the tungsten oxide particles (W) and the dispersant particles (X) were changed as described in table 3. The evaluation results of the resin molded bodies are shown in table 3.
TABLE 3
Figure GDA0002920607130000421
*1 content ratio relative to the total mass of the (meth) acrylic polymer (P)
Example 16
92 parts by mass of the slurry (Z) produced in example 1, 8 parts by mass of MMA, and,0.1 part by mass of the dispersant copolymer (X-1) produced in production example 3, 0.03 part by mass (containing 6.9X10) -3 Tungsten oxide particles) as tungsten oxide particles (W-1) and 0.4 parts by mass of HPP as a polymerization initiator, and the resultant was dissolved as a polymerizable composition (M2).
Under the same production conditions as in example 1, a plate-like resin molded article having a thickness of 3mm was obtained. The evaluation results of the obtained resin molded bodies are shown in table 4.
Examples 17 to 22
Resin molded articles were obtained in the same manner as in example 16, except that the blending amount of the tungsten oxide particles (W) or the dispersant particles (X) was changed as shown in table 4. The evaluation results of the resin molded bodies are shown in table 4.
Comparative example 8
A resin molded article was obtained in the same manner as in example 16, except that the dispersant particles (X) were not used. The evaluation results of the resin molded bodies are shown in table 4.
Comparative example 9
A resin molded article was obtained in the same manner as in example 16, except that the tungsten oxide particles (W) were not used. The evaluation results of the resin molded bodies are shown in table 4.
Comparative example 10
Resin molded articles were obtained in the same manner as in example 1 except that the dispersant copolymer (X-1) of the dispersant particles (X) was changed to the dispersant copolymer (X-2) and the blending amount was changed as shown in Table 4. The evaluation results of the resin molded bodies are shown in table 4.
TABLE 4
Figure GDA0002920607130000441
/>
In the resin molded articles of examples 1 to 15, tungsten oxide particles (W) were adsorbed on the particle surfaces of the dispersant particles (X) to form composite particles (XW). Therefore, the resin molded articles of examples 1 to 15 were excellent in transparency, low coloring property and heat ray shielding property.
The resin molded articles of comparative examples 1 and 2 did not contain the dispersant particle (X). Therefore, in the resin molded articles of comparative examples 1 and 2, the tungsten oxide particles (W) formed agglomerated particles, which were insufficient in transparency and large in coloration.
The resin molded articles of comparative examples 3 and 4 did not contain tungsten oxide particles (W). Therefore, the resin molded articles of comparative examples 3 and 4 were poor in heat ray shielding property.
The resin molded articles of comparative examples 5 to 7 each contained the copolymers (D-3) to (D-5) which did not form the composite particles (XW) as other dispersants instead of the dispersant particles (X). Therefore, the resin molded articles of comparative examples 5 to 7 were large in coloring.
The resin molded articles of examples 16 to 22 contain (meth) acrylic polymer (P), tungsten oxide particles (W) and dispersant particles (X). Therefore, the resin molded articles of examples 16 to 22 were excellent in transparency, low coloring property and heat ray shielding property.
The resin molded article of comparative example 8 contained no dispersant particle (X). Therefore, the resin molded article of comparative example 8 was large in coloring.
The resin molded article of comparative example 9 did not contain tungsten oxide particles (W). Therefore, the resin molded article of comparative example 9 was poor in heat ray shielding property.
The resin molded article of comparative example 10 contained the dispersant copolymer (X-2) which did not form composite particles (XW) as another dispersant in place of the dispersant particles (X). Therefore, the resin molded article of comparative example 10 was insufficient in transparency and large in coloration.
Industrial applicability
The resin molded article of the present invention is excellent in transparency, low coloring property and heat ray shielding property, and thus can be suitably used as a protective material for a ceiling material, a window material, illumination, and a signboard used in a building, an automobile, a train, or a bus.
Symbol description
1. Tungsten oxide particles (W)
2. Dispersant particle (X) (particle-like copolymer (D))
3. Composite particles (XW)
4 (meth) acrylic polymer (P).

Claims (22)

1. A resin molded article comprising a resin composition containing a transparent resin, tungsten oxide particles (W) and dispersant particles (X),
the dispersant particles (X) are a particulate copolymer (D) having a crosslinked structure,
the resin molded article contains composite particles (XW) having at least one of a form in which tungsten oxide particles (W) are present on the particle surfaces of dispersant particles (X) and a form in which a plurality of tungsten oxide particles (W) are contained in the interior of the particles of dispersant particles (X),
the dispersion particle diameter of the composite particles (XW) is 100nm to 1000 nm.
2. A resin molded article comprising a resin composition containing a transparent resin, tungsten oxide particles (W) and dispersant particles (X),
The dispersant particles (X) are a particulate copolymer (D) having a crosslinked structure,
the resin molded body contains composite particles (XW) containing the tungsten oxide particles (W) and the dispersant particles (X),
the dispersion particle diameter of the composite particles (XW) is 100nm to 1000 nm.
3. The resin molded article according to claim 2, wherein the composite particles (XW) have at least one of a form in which tungsten oxide particles (W) are present on the particle surfaces of the dispersant particles (X) and a form in which a plurality of tungsten oxide particles (W) are contained in the particles of the dispersant particles (X).
4. The resin molded body according to any one of claims 1 to 3, wherein the tungsten oxide particles (W) are contained in an amount of 0.05g/m per unit area of the projected area of the resin molded body 2 Above 3.00g/m 2 The following is given.
5. The resin molded body according to any one of claims 1 to 3, wherein the transparent resin is a (meth) acrylic polymer (P), and the resin composition is a (meth) acrylic resin composition.
6. A resin molded article comprising a (meth) acrylic resin composition containing a (meth) acrylic polymer (P), tungsten oxide particles (W) and dispersant particles (X),
The dispersant particles (X) are a particulate copolymer (D) having a crosslinked structure,
the resin molded article contains composite particles (XW) having at least one of a form in which tungsten oxide particles (W) are adsorbed on the particle surfaces of dispersant particles (X) and a form in which a plurality of tungsten oxide particles (W) are contained in the interior of the particles of dispersant particles (X),
the composite particles (XW) have a dispersed particle diameter of 100nm to 1000nm,
the tungsten oxide particles (W) content of the resin molded body per unit area of the projected area of the resin molded body is 0.05g/m 2 Above 3.00g/m 2 The following is given.
7. The resin molded body according to any one of claims 1 to 3 and 6,
the composite particles (XW) contain composite particles (XW 1), and the composite particles (XW 1) have a morphology in which the tungsten oxide particles (W) are present on the particle surfaces of the dispersant particles (X).
8. A resin molded article comprising a (meth) acrylic resin composition containing a (meth) acrylic polymer (P), tungsten oxide particles (W) and dispersant particles (X),
the dispersant particles (X) are a particulate copolymer (D) having a crosslinked structure,
The resin molded body is formed with composite particles (XW 1), the composite particles (XW 1) are formed by adsorbing the tungsten oxide particles (W) on the particle surfaces of the dispersant particles (X),
the dispersion particle diameter of the composite particles (XW 1) is 100nm to 1000 nm.
9. The resin molded article according to claim 8, wherein the particulate copolymer (D) is a multistage polymerized copolymer comprising:
rubbery copolymer having a crosslinked structure; and
an outer layer polymer (C) obtained by polymerizing a monomer mixture containing at least one of an alkyl acrylate (a 1) having an alkyl group having 1 to 8 carbon atoms and an alkyl methacrylate (a 2) having an alkyl group having 1 to 8 carbon atoms in the presence of the rubber-like copolymer.
10. The resin molded body according to claim 9, wherein the rubbery copolymer has:
an intermediate layer polymer (B) obtained by polymerizing a monomer mixture containing an alkyl acrylate (a 1) having an alkyl group having 1 to 8 carbon atoms, an aromatic vinyl compound (a 3), and a polyfunctional monomer (a 5).
11. The resin molded body according to claim 9 or 10, the rubbery copolymer having:
an innermost polymer (A) obtained by polymerizing a monomer mixture containing an alkyl acrylate (a 1) having an alkyl group having 1 to 8 carbon atoms, an alkyl methacrylate (a 4) having an alkyl group having 1 to 4 carbon atoms, an aromatic vinyl compound (a 3), and a polyfunctional monomer (a 5); and
An intermediate layer polymer (B) obtained by polymerizing a monomer mixture comprising an alkyl acrylate (a 1) having an alkyl group having 1 to 8 carbon atoms, an aromatic vinyl compound (a 3) and a polyfunctional monomer (a 5) in the presence of the innermost layer polymer (A).
12. The resin molded article according to claim 7, wherein the particulate copolymer (D) is a multistage polymerized copolymer comprising:
rubbery copolymer having a crosslinked structure; and
an outer layer polymer (C) obtained by polymerizing a monomer mixture containing at least one of an alkyl acrylate (a 1) having an alkyl group having 1 to 8 carbon atoms and an alkyl methacrylate (a 2) having an alkyl group having 1 to 8 carbon atoms in the presence of the rubber-like copolymer.
13. The resin molded article according to any one of claims 1 to 3, 6, 8, 9, and 10, wherein the composite particles (XW) in the (meth) acrylic resin composition are dispersed substantially in a one-time dispersion.
14. The resin molded article according to claim 4, wherein the composite particles (XW) in the (meth) acrylic resin composition are dispersed substantially in a one-time dispersion.
15. The resin molded article according to claim 5, wherein the composite particles (XW) in the (meth) acrylic resin composition are dispersed substantially in a one-time dispersion.
16. The resin molded article according to claim 7, wherein the composite particles (XW) in the (meth) acrylic resin composition are substantially dispersed in a one-shot dispersion.
17. The resin molded article according to claim 11, wherein the composite particles (XW) in the (meth) acrylic resin composition are substantially dispersed in a one-shot dispersion.
18. The resin molded article according to claim 12, wherein the composite particles (XW) in the (meth) acrylic resin composition are substantially dispersed in a one-shot dispersion.
19. A resin molded article comprising a resin composition containing a transparent resin, tungsten oxide particles (W) and dispersant particles (X),
the dispersant particles (X) are a particulate copolymer (D) having a crosslinked structure,
the resin molded article contains composite particles (XW) having at least one of a form in which tungsten oxide particles (W) are present on the particle surfaces of dispersant particles (X) and a form in which a plurality of tungsten oxide particles (W) are contained in the interior of the particles of dispersant particles (X),
the composite particles (XW) have a dispersed particle diameter of 100nm to 1000nm, and
the total light transmittance measured in accordance with JIS K7361-1 in the wavelength range of 380 to 780nm is 60% or more,
The haze measured in accordance with JIS K7136 in the wavelength range of 380 to 780nm is 10% or less, the Yellow Index (YI) in the thickness direction measured in accordance with ASTM D1925 is less than 4.0, and the heat ray blocking rate measured in the wavelength range of 780 to 2100nm is 40% or more.
20. A heat ray shielding plate comprising the resin molded body according to any one of claims 1 to 19.
21. A ceiling material comprising the resin molded body according to any one of claims 1 to 19.
22. A window material comprising the resin molded body according to any one of claims 1 to 19.
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TW200922983A (en) * 2006-07-25 2009-06-01 Sumitomo Metal Mining Co Highly heat-resistant masterbatch, heat ray-shielding transparent resin molding, and heat ray-shielding transparent laminate
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