JP7010832B2 - Glass laminate - Google Patents

Description

The present invention relates to a laminate (also referred to as a glass laminate) in which a hard resin sheet containing a layer made of a methacrylic resin composition containing light diffusing particles is bonded to a glass plate via an adhesive layer.

Conventionally, the development of a glass laminate in which a transparent resin sheet is laminated on a glass plate has been promoted for the purpose of reducing the weight and improving the safety of glass members such as automobile glazing. Furthermore, in recent years, studies have begun on a planar light emitter that applies a light guide method by combining a light source with a glass laminate. Such a planar light emitter functions like a transparent plate when the light source is turned off, can function as lighting when the light source is turned on, and can be preferably used for high-performance automobile glazing and the like.

Among the transparent resins, methacrylic resin is particularly excellent in transparency, scratch resistance, weather resistance, etc., and is suitable as a resin material for a glass laminate. However, in general, the methacrylic resin has a low glass transition temperature (Tg) of about 110 ° C. Therefore, the glass laminate using the methacrylic resin may cause poor appearance or deformation due to heat during the laminating process of the methacrylic resin sheet and the glass plate or in the actual use environment of the glass laminate.

Conventionally, as a method of increasing the glass transition temperature (Tg) of a material containing a methacrylic resin, a method of increasing the syndiotacticity of the methacrylic resin (for example, Patent Document 1), and styrene and maleic acid anhydride in the methacrylic resin are used. A method of blending a copolymer resin (for example, Patent Document 2) and the like are known. Further, a glass laminate containing a layer made of a methacrylic resin composition containing a copolymer resin of styrene and maleic anhydride and a glass layer is disclosed (for example, Patent Document 3).

Japanese Unexamined Patent Publication No. 3-263421 Japanese Unexamined Patent Publication No. 2015-105371 International Publication No. 2014/187500

However, when the glass laminate described in Patent Document 3 is surface-emitting using a light guide method, the light cannot be sufficiently scattered and it is difficult to obtain a high-brightness planar emitter.
An object of the present invention is to provide a glass laminate excellent in light weight, transparency, durability, and light guide performance.

As a result of studies for achieving the above object, the present inventor has completed the present invention including the following embodiments.
[1] A laminate having a glass plate arranged via an adhesive layer on one surface of a hard resin sheet.
A laminate containing a layer of a methacrylic resin composition in which the hard resin sheet contains a methyl methacrylate (co) polymer and light diffusing particles and has a glass transition temperature of 120 ° C. or higher.

[2] The methyl methacrylate (co) polymer comprises 60 to 100% by mass of a methyl methacrylate unit and 40 to 0% by mass of a (meth) acrylic acid ester unit other than methyl methacrylate. The laminate of [1] containing the coalescence (A).
[3] The methyl methacrylate (co) polymer (A) is a laminate of [2] having a syndiotacticity (rr) of 58 to 85% in triplet representation.
[4] The methyl methacrylate (co) polymer is methyl methacrylate consisting of 10 to 35% by mass of the methyl methacrylate unit, 15 to 40% by mass of the maleic anhydride unit, and 50 to 75% by mass of the aromatic vinyl compound unit. The laminate of [1] containing the copolymer (B).

[5] The methacrylic resin composition is
5 to 80% by mass of the methyl methacrylate (co) polymer (A) consisting of 60 to 100% by mass of the methyl methacrylate unit and 40 to 0% by mass of the (meth) acrylic acid ester unit other than methyl methacrylate, and
It contains 95 to 20% by mass of the methyl methacrylate copolymer (B) consisting of 10 to 35% by mass of the methyl methacrylate unit, 15 to 40% by mass of the maleic anhydride unit and 50 to 75% by mass of the aromatic vinyl compound unit [1]. ] To [4].

[6] The laminate according to any one of [1] to [5], wherein the methacrylic resin composition contains 0.00005 to 0.1% by mass of the light diffusing particles.
[7] Any of [1] to [6], wherein the absolute value of the refractive index difference (Δn) between the refractive index of the matrix resin of the methacrylic resin composition and the refractive index of the light diffusing particles is 0.3 to 3. The laminated body.
[8] The laminate according to any one of [1] to [7], wherein the product of the absolute value of the refractive index difference (Δn) and the volume average particle diameter d (μm) of the light diffusing particles is 0.1 μm or more. ..
[9] The laminate according to any one of [1] to [8], wherein the methacrylic resin composition contains 0.0001 to 0.01% by mass of a bluing agent.

[10] The hard resin sheet is a laminated sheet including a layer made of the methacrylic resin composition and a layer made of another thermoplastic resin.
The laminate according to any one of [1] to [9], wherein the laminate has the adhesive layer on the surface of a layer made of the other thermoplastic resin.
[11] The laminate according to any one of [1] to [10], wherein the soft resin constituting the adhesive layer is thermoplastic polyurethane.
[12] Further, any of the laminates [1] to [11] having a scratch resistant layer on the other surface of the rigid resin sheet of the laminate.

[13] A vehicle member including the laminate according to any one of [1] to [12].
[14] An automobile glazing material containing the laminate according to any one of [1] to [12].
[15] An automobile sunroof material containing the laminate according to any one of [1] to [12].

According to the present invention, it is possible to provide a glass laminate excellent in light weight, transparency, durability, and light guide performance.

It is a schematic sectional drawing of the glass laminated body of 1st Embodiment which concerns on this invention. It is a schematic sectional drawing of the glass laminated body of 2nd Embodiment which concerns on this invention. It is a schematic sectional drawing of the glass laminated body of 3rd Embodiment which concerns on this invention. It is a schematic sectional drawing of the glass laminated body of 4th Embodiment which concerns on this invention. It is a schematic cross-sectional view of the evaluation system of the planar illuminant produced in the section of [Example].

Hereinafter, the present invention will be described in detail.
[Glass laminate]
The glass laminate of the present invention has a multilayer structure in which a glass plate is laminated on one surface of a hard resin sheet via an adhesive layer containing a soft resin. In the glass laminate of the present invention, the hard resin sheet is a layer composed of a methacrylic resin composition containing a methyl methacrylate (co) polymer and light diffusing particles and having a glass transition temperature (Tg) of 120 ° C. or higher (hereinafter,). Also referred to as a "methacrylic resin composition layer").
The glass laminate of the present invention can be suitably used as a window glass member for vehicles, a window glass member for buildings, a glass member for doors, and the like.

Hereinafter, the structure of the glass laminate according to the first to fourth embodiments according to the present invention will be described. In these embodiments, the same components are designated by the same reference numerals.
FIG. 1 shows a schematic cross-sectional view of the glass laminate of the first embodiment. In the figure, reference numeral 10X is a glass laminate of the present embodiment, reference numeral R1 is a hard resin sheet made of a methacrylic resin composition layer 11, reference numeral 12 is an adhesive layer, and reference numeral 13 is a glass plate.
The glass laminate of the present invention is not limited to the three-layer structure. The hard resin sheet R1 includes one or more layers of the methacrylic resin composition layer 11 and, if necessary, a layer made of a thermoplastic resin (composition) other than the methacrylic resin composition (hereinafter, “other heat”). It can also include any one or more layers such as "plastic resin (composition) layer". " The glass laminate of the present invention may contain a plurality of hard resin sheets R1, a plurality of adhesive layers 12, and a plurality of glass plates 13. Further, the stacking order of at least one layer of the hard resin sheet R1, at least one layer of the adhesive layer 12, and at least one layer of the glass plate 13 is appropriately designed. The glass laminate of the present invention may contain any other one or more layers.

FIG. 2 shows a schematic cross-sectional view of the glass laminate of the second embodiment. This glass laminate is an embodiment including a layer made of a thermoplastic resin (composition) other than the methacrylic resin composition. In the figure, reference numeral 10Y indicates the glass laminate of the present embodiment, and reference numeral 14 indicates another thermoplastic resin (composition) layer. Reference numerals 11 to 13 are the same as those in FIG.
The glass laminate 10Y of the present embodiment includes a hard resin sheet R2 composed of a methacrylic resin composition layer 11 and another thermoplastic resin (composition) layer 14. The design of the embodiment including a layer made of a thermoplastic resin (composition) other than the methacrylic resin composition can be appropriately changed.

3 and 4 show schematic cross-sectional views of the glass laminates of the third and fourth embodiments, respectively. Each of these glass laminates is an embodiment including a scratch resistant layer. In the figure, reference numeral 20X indicates a glass laminate of the third embodiment, reference numeral 20Y indicates a glass laminate of the fourth embodiment, and reference numeral 21 indicates a scratch resistant layer. Reference numerals 10X, 10Y, 11 to 14 are the same as those in FIGS. 1 and 2. The design including the scratch-resistant layer can be changed as appropriate.

(Hard resin sheet)
The hard resin sheet constituting the glass laminate of the present invention is a layer composed of a methacrylic resin composition containing a methyl methacrylate (co) polymer and light diffusing particles and having a glass transition temperature (Tg) of 120 ° C. or higher. (Methyl resin composition layer) is included.
<Methyl methacrylate (co) polymer>
The hard resin sheet contains one or more methyl methacrylate (co) polymers. The methyl methacrylate (co) polymer is polymethyl methacrylate (PMMA), which is a homopolymer of methyl methacrylate (MMA), or the copolymerization of MMA and one or more other monomers. It is a coalescence.

The methacrylic resin composition comprises a methyl methacrylate (co) polymer (A) consisting of 60 to 100% by mass of methyl methacrylate (MMA) unit and 40 to 0% by mass of (meth) acrylic acid ester units other than methyl methacrylate. It is preferable to include it. The hard resin sheet containing the methyl methacrylate (co) polymer (A) is excellent in scratch resistance and is preferable.
The content of the MMA monomer unit in the methyl methacrylate (co) polymer (A) is 60% by mass or more, preferably 80% by mass or more, more preferably 80% by mass or more because the hard resin sheet has excellent scratch resistance. It is 90% by mass or more, particularly preferably 99% by mass or more, and most preferably 100% by mass.
The content of the MMA monomer unit in the methyl methacrylate (co) polymer is purified by reprecipitating the methyl methacrylate (co) polymer in methanol and then pyrolyzed using pyrolysis gas chromatography. And the volatile component is separated, and it can be calculated from the ratio of the peak area of the MMA and the copolymerized component.

The methyl methacrylate (co) polymer (A) can contain (meth) acrylic acid ester units other than MMA in all the monomer units. Examples of the (meth) acrylic acid ester unit other than MMA include ethyl methacrylate, n-propyl methacrylate, isopropyl methacrylate, n-butyl methacrylate, isobutyl methacrylate, tert-butyl methacrylate, pentyl methacrylate, and hexyl methacrylate. Alkyl methacrylate esters such as heptyl methacrylate, 2-ethylhexyl methacrylate, nonyl methacrylate, decyl methacrylate, and dodecyl methacrylate; 1-methylcyclopentyl methacrylate, cyclohexyl methacrylate, cycloheptyl methacrylate, cyclooctyl methacrylate. Cycloalkyl esters of methacrylic acid such as tricyclomethacrylate [5.2.1.0 ^2,6 ] deca-8-yl (TCDMA); aryl methacrylate esters such as phenyl methacrylate; methacrylic acid such as benzyl methacrylate. Aralkyl ester; methyl acrylate (MA), ethyl acrylate, n-propyl acrylate, isopropyl acrylate, n-butyl acrylate, isobutyl acrylate, tert-butyl acrylate, hexyl acrylate, 2-ethylhexyl acrylate, Nonyl acrylate, decyl acrylate, dodecyl acrylate, stearyl acrylate, 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, 4-hydroxybutyl acrylate, cyclohexyl acrylate, 2-methoxyethyl acrylate, acrylate 3-methoxybutyl, trifluoromethyl acrylate, trifluoroethyl acrylate, pentafluoroethyl acrylate, glycidyl acrylate, allyl acrylate, phenyl acrylate, toluyl acrylate, benzyl acrylate, isobornyl acrylate, and acrylate. Examples thereof include acrylic acid esters such as 3-dimethylaminoethyl. From the viewpoint of availability and heat resistance, TCDMA and MA are preferable.

The content of the (meth) acrylic acid ester unit other than the MMA unit in the methyl methacrylate (co) polymer (A) is 40% by mass or less, preferably 20% by mass or less, more preferably 10% by mass or less, particularly preferably. Is less than 1%. The methyl methacrylate (co) polymer (A) may not contain (meth) acrylic acid ester units other than MMA.

The methyl methacrylate (co) polymer (A) can be obtained by polymerizing MMA and, if necessary, other monomers. When polymerization is carried out using a plurality of types of monomers, usually, a plurality of types of monomers are mixed to prepare a monomer mixture, which is then subjected to polymerization. The polymerization method is not particularly limited, but radical polymerization and anionic polymerization are preferable from the viewpoint of productivity and heat resistance.

From the viewpoint of heat resistance, the lower limit of the syndiotacticity (rr) of the triplet display of the methyl methacrylate (co) polymer (A) is preferably 50% or more, more preferably 55% or more, and particularly preferably. Is 58% or more, most preferably 60% or more. From the viewpoint of sheet formability, the upper limit of the syndiotacticity (rr) of the triplet display of the methyl methacrylate (co) polymer (A) is preferably 99%, more preferably 85%, and particularly preferably. 77%, most preferably 65%.

Here, the syndiotacticity (rr) in triplet representation (also simply referred to as "syngiotacticity (rr)" or "rr ratio") is a chain of three consecutive structural units (triplet, triad). ) Has two chains (double element, diad), both of which are racemic (denoted as rr). In the chain of structural units (double element, diad) in the polymer molecule, those having the same configuration are referred to as meso, and the opposite ones are referred to as racemo, which are referred to as m and r, respectively.
The rr ratio (%) of the methyl methacrylate (co) polymer (A) is ¹ H-NMR spectrum measured at 30 ° C. in deuterated chloroform, and tetramethylsilane (TMS) is 0 ppm from the spectrum. The area (X) of the region of 0.6 to 0.95 ppm and the area (Y) of the region of 0.6 to 1.35 ppm were measured and calculated by the formula: (X / Y) × 100. can do.

The weight average molecular weight (Mw) of the methyl methacrylate (co) polymer (A) is preferably 40,000 to 500,000, more preferably 60,000 to 300,000, and particularly 80,000 to 200,000. preferable. When Mw is 40,000 or more, the glass laminate of the present invention has excellent mechanical strength, and when Mw is 500,000 or less, the glass laminate of the present invention has excellent moldability. ..

The glass transition temperature (Tg) of the methyl methacrylate (co) polymer (A) is preferably 100 ° C. or higher, more preferably 110 ° C. or higher, and particularly preferably 120 ° C. or higher. When the Tg is 100 ° C. or higher, the methacrylic resin composition has excellent heat resistance.
When the methacrylic resin composition contains a plurality of types of methyl methacrylate (co) polymers, the glass transition temperature (Tg) of the entire methacrylic resin composition may be 120 ° C. or higher, which constitutes the methacrylic resin composition. The glass transition temperature (Tg) of some methyl methacrylate (co) polymers may be less than 120 ° C.
The glass transition temperature (Tg) in the present specification is a value calculated by the midpoint method by measuring with a differential scanning calorimeter under the condition of a heating rate of 10 ° C./min.

The melt flow rate (MFR) of the methyl methacrylate (co) polymer (A) is preferably in the range of 1 to 10 g / 10 minutes. The lower limit of MFR is more preferably 1.2 g / 10 minutes, and particularly preferably 1.5 g / 10 minutes. Further, the upper limit of MFR is more preferably 7.0 g / 10 minutes, and particularly preferably 4.0 g / 10 minutes. When the MFR is in the range of 1 to 10 g / 10 minutes, the stability of heat melt molding is good. The MFR in the present specification is a value measured using a melt indexer at a temperature of 230 ° C. under a load of 3.8 kg.

The methacrylic resin composition is a methyl methacrylate (MMA) unit of 10-35 mass, in place of the methyl methacrylate (co) polymer (A) or in combination with the methyl methacrylate (co) polymer (A). Methyl methacrylate copolymer (B) consisting of%, 15 to 40% by mass of maleic anhydride unit, and 50 to 75% by mass of aromatic vinyl compound unit can be contained.

The content of MMA units in the methyl methacrylate copolymer (B) is preferably 1% by mass or more, more preferably 3% by mass or more, and particularly preferably 5% by mass or more. Most preferably, it is 10% by mass or more. The content of MMA units in the methyl methacrylate copolymer (B) is preferably 35% by mass or less, more preferably 30% by mass or less, and particularly preferably 26% by mass or less. When the content of the MMA unit is in the range of 1 to 35% by mass, the methacrylic resin composition is excellent in transparency and thermal stability.

The content of the maleic anhydride unit in the methyl methacrylate copolymer (B) is preferably 15% by mass or more, more preferably 18% by mass or more, and particularly preferably 20% by mass or more. preferable. The content of the maleic anhydride unit in the methyl methacrylate copolymer (B) is preferably 49% by mass or less, more preferably 45% by mass or less, and particularly preferably 40% by mass or less. .. When the content of the maleic anhydride unit is in the range of 15 to 49% by mass, the methacrylic resin composition is excellent in heat resistance and transparency.

The content of the aromatic vinyl compound unit in the methyl methacrylate copolymer (B) is preferably 50% by mass or more, more preferably 55% by mass or more, and particularly preferably 60% by mass or more. preferable. The content of the aromatic vinyl compound unit in the methyl methacrylate copolymer (B) is preferably 84% by mass or less, more preferably 82% by mass or less, and particularly preferably 80% by mass or less. preferable. When the content of the aromatic vinyl compound unit is in the range of 50 to 84% by mass, the methacrylic resin composition is excellent in moisture resistance and transparency.

Aromatic vinyl compounds include, for example, styrene; alkyl-substituted styrenes such as 2-methylstyrene, 3-methylstyrene, 4-methylstyrene, 4-ethylstyrene, and 4-tert-butylstyrene; α-methylstyrene, and 4 Examples thereof include α-alkyl substituted styrene such as -methyl-α-methylstyrene. Styrene is preferred from the viewpoint of availability. One or more of these aromatic vinyl compounds can be used.

The methyl methacrylate copolymer (B) may have structural units derived from other monomers other than MMA, maleic anhydride, and aromatic vinyl compounds. Other monomers include MA, ethyl acrylate, n-propyl acrylate, isopropyl acrylate, n-butyl acrylate, isobutyl acrylate, tert-butyl acrylate, hexyl acrylate, 2-ethylhexyl acrylate, Nonyl acrylate, decyl acrylate, dodecyl acrylate, stearyl acrylate, 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, 4-hydroxybutyl acrylate, cyclohexyl acrylate, 2-methoxyethyl acrylate, acrylate 3-methoxybutyl, trifluoromethyl acrylate, trifluoroethyl acrylate, pentafluoroethyl acrylate, glycidyl acrylate, allyl acrylate, phenyl acrylate, toluyl acrylate, benzyl acrylate, isobornyl acrylate, and acrylate Examples thereof include acrylic acid esters such as 3-dimethylaminoethyl. These other monomers may be used alone or in combination of two or more. The content of the other monomer unit in the methyl methacrylate copolymer (B) is preferably 10% by mass or less, more preferably 5% by mass or less, and particularly preferably 2% by mass or less.

The methyl methacrylate copolymer (B) is obtained by polymerizing MMA, maleic anhydride, an aromatic vinyl compound, and, if necessary, other monomers. In this polymerization, usually, a plurality of kinds of monomers are mixed to prepare a monomer mixture, which is then subjected to polymerization. The polymerization method is not particularly limited, but from the viewpoint of productivity, a method of radical polymerization by a method such as a bulk polymerization method or a solution polymerization method is preferable.

The Mw of the methyl methacrylate copolymer (B) is preferably in the range of 40,000 to 300,000. When Mw is 40,000 or more, the methacrylic resin composition has excellent mechanical strength. When Mw is 300,000 or less, the moldability of the methacrylic resin composition can be improved.

The glass transition temperature (Tg) of the methyl methacrylate copolymer (B) is preferably 115 ° C. or higher, more preferably 120 ° C. or higher, and particularly preferably 125 ° C. or higher. When the glass transition temperature (Tg) is 115 ° C. or higher, the methacrylic resin composition has excellent heat resistance, and it is possible to suppress appearance defects and deformation of the glass laminate due to heat.

The MFR of the methyl methacrylate copolymer (B) is preferably in the range of 1 to 10 g / 10 minutes. The lower limit of MFR is more preferably 1.2 g / 10 minutes, and particularly preferably 1.5 g / 10 minutes. The upper limit of MFR is more preferably 7.0 g / 10 minutes, and particularly preferably 4.0 g / 10 minutes. When the MFR is in the range of 1 to 10 g / 10 minutes, the stability of heat melt molding is good.

The hard resin sheet preferably contains a methacrylic resin composition layer containing a methyl methacrylate (co) polymer (A) and a methyl methacrylate copolymer (B). The mass ratio (mass ratio (A) / (B)) of the methyl methacrylate (co) polymer (A) to the methyl methacrylate copolymer (B) is a viewpoint of heat resistance, transparency, and scratch resistance. It is preferably in the range of 5/95 to 90/10. The mass ratio (A) / (B) is more preferably 10/90 or more, particularly preferably 15/85 or more, and most preferably 20/80 or more. Further, the mass ratio (A) / (B) is more preferably 85/15 or less, particularly preferably 80/20 or less, and most preferably 75/25 or less.

Examples of the mixing method of the methyl methacrylate (co) polymer (A) and the methyl methacrylate copolymer (B) include a melt mixing method and a solution mixing method. In the melt mixing method, for example, a uniaxial or multiaxial kneader, an open roll, a Banbury mixer, and a melt kneader such as a kneader are used, and if necessary, an inert gas such as nitrogen gas, argon gas, and helium gas is used. Melting and kneading can be performed in an atmosphere. In the solution mixing method, the methyl methacrylate (co) polymer (A) and the methyl methacrylate copolymer (B) can be dissolved in an organic solvent such as toluene, tetrahydrofuran, and methyl ethyl ketone and mixed.

The methacrylic resin composition may contain a polymer other than the methyl methacrylate (co) polymer (A) and the methyl methacrylate copolymer (B) as long as the effects of the present invention are not impaired. .. Other polymers include polyolefin resins such as polyethylene, polypropylene, polybutene-1, poly-4-methylpentene-1, and polynorbornene, ethylene-based ionomers; polystyrene, styrene-maleic anhydride copolymers, high-impact polystyrene. , AS resin, ABS resin, AES resin, AAS resin, ACS resin, MBS resin and other styrene resins; methyl methacrylate-styrene copolymer; polyethylene terephthalate, and polybutylene terephthalate and other polyester resins; nylon 6, nylon 66. , And polyamide resins such as polyamide elastomers; polyphenylene sulfide, polyether ether ketone, polysulfone, polyphenylene oxide, polyimide, polyetherimide, polycarbonate, polyvinyl chloride, polyvinylidene chloride, polyvinylidene fluoride, polyvinyl alcohol, ethylene-vinyl alcohol. Other thermoplastic resins such as polymers, polyacetals, polyurethanes, phenoxy resins, modified polyphenylene ethers, and silicone modified resins; thermocurable resins such as phenolic resins, melamine resins, silicone resins, and epoxy resins; acrylic rubber, silicone rubber Styrene-based thermoplastic polymers such as SEPS, SEBS, and SIS; olefin-based rubbers such as IR, EPR, and EPDM. These can be used alone or in combination of two or more.
The content of the other polymer in the methacrylic resin composition is preferably 10% by mass or less, more preferably 5% by mass or less, and particularly preferably 2% by mass or less.

The methacrylic resin composition constituting the hard resin sheet of the glass laminate of the present invention contains light diffusing particles. The light diffusing particles have a refractive index different from that of the methyl methacrylate (co) polymer, which is a matrix resin (base resin other than the light diffusing particles) of the hard resin sheet, and are particles that scatter light. Since the hard resin sheet contains light-diffusing particles, the glass laminate of the present invention faces each other while scattering light in the thickness direction of the glass laminate when light is introduced from a light source to one end surface of the glass laminate. It is possible to guide light toward the other end surface in the surface direction of the laminated body. In the embodiment in which the light diffusing particles are contained in the hard resin sheet, it is possible to provide a laminate having excellent light guide performance at low cost without the need to separately provide a light diffusing layer by printing, surface unevenness processing, or the like.

The concentration of the light diffusing particles in the methacrylic resin composition is preferably 0.00005 to 0.1% by mass, more preferably 0.0001 to 0.01% by mass, and 0.0002 to 0. It is particularly preferable that it is 001% by mass. The higher the concentration of the light diffusing particles, the lower the transparency of the glass laminate containing the hard resin sheet tends to be. Therefore, in order to keep the haze value of the hard resin sheet low, it is preferable to keep the concentration of the light diffusing particles low. On the other hand, if the concentration of the light diffusing particles is too low, the light cannot be sufficiently scattered when the light is introduced into the hard resin sheet from the light source, and the light guide performance of the glass laminate may be insufficient. .. When the concentration of the light diffusing particles in the methacrylic resin composition is in the range of 0.00005 to 0.1% by mass, both good transparency and good light guide performance can be achieved at the same time.

The volume average particle size (volume average diameter) d of the light diffusing particles is preferably 0.5 to 5 μm, more preferably 0.75 to 4 μm, and particularly preferably 1 to 3 μm. When the volume average particle size d of the light diffusing particles is smaller than 0.5 μm, there may be a difference in color between the vicinity of the light incident end face of the glass laminate and the position away from the light incident end face. When the volume average particle size d of the light diffusing particles is larger than 5 μm, the light diffusing particles having a relatively large particle size may become bright spots when the light source is turned on and spoil the appearance. The volume average particle size d in the present specification is the particle size obtained by taking an electron micrograph of the primary particles and using image analysis type particle size distribution measurement software.

In the methacrylic resin composition, the difference in refractive index (Δn) between the methyl methacrylate (co) polymer as the matrix resin and the light diffusing particles is preferably 0.3 to 3. When the refractive index difference (Δn) is smaller than 0.3, light cannot be efficiently extracted, and the transparency may be inferior for the brightness when the light source is lit. The refractive index difference (Δn) is more preferably 0.4 or more. On the other hand, when the refractive index difference (Δn) is larger than 3, backscattering is dominant in the scattered light, so that the light cannot be efficiently extracted, and the transparency is inferior for the brightness when the light source is lit. In some cases.

As the light diffusing particles, inorganic compound particles having a large difference in refractive index with respect to the matrix resin are preferably used, and for example, titanium oxide and zinc oxide are preferably used.

If the volume average particle size d of the light diffusing particles is too small, a change in color such as coloring, which is considered to be caused by the Rayleigh scattering phenomenon, may occur. Further, even when the difference in refractive index (Δn) is too small, a change in color such as coloring, which is considered to be caused by the Rayleigh scattering phenomenon, may occur. Specifically, the scattered light may be bluish in the vicinity of the light source and yellowish in the vicinity of the light source.
In order to suppress changes in color such as coloring that are thought to be caused by the Rayleigh scattering phenomenon, the product of the volume average particle size d (μm) of the light diffusing particles and the absolute value of the refractive index difference (Δn) (| Δn | ) Is preferably 0.1 μm or more.

The methacrylic resin composition may contain various additives in addition to the light diffusing particles, if necessary. Additives include, for example, antioxidants, heat deterioration inhibitors, UV absorbers, light stabilizers, lubricants, mold release agents, polymer processing aids, antistatic agents, flame retardants, brewing agents, matting agents, etc. Examples thereof include impact resistance modifiers and phosphors. The methacrylic resin composition preferably contains 0.0001 to 0.01% by mass of a bluing agent for color matching.

When an arbitrary component such as another polymer and an additive is added to the methacrylic resin composition, the timing of addition of the optional component is not particularly limited, and the methyl methacrylate (co) polymer (A) and / or methyl methacrylate The timing may be any of the timing of the polymerization of the copolymer (B), the mixing of the polymerized methyl methacrylate (co) polymer (A) and the methyl methacrylate copolymer (B), or after mixing.

The glass transition temperature (Tg) of the methacrylic resin composition is 120 ° C. or higher, preferably 130 ° C. or higher, and more preferably 140 ° C. or higher. When the glass transition temperature (Tg) is 120 ° C. or higher, the methacrylic resin composition has excellent heat resistance.

The MFR of the methacrylic resin composition is preferably in the range of 1 to 10 g / 10 minutes. The lower limit of MFR is more preferably 1.2 g / 10 minutes, and particularly preferably 1.5 g / 10 minutes. Further, the upper limit of MFR is more preferably 7.0 g / 10 minutes, and particularly preferably 4.0 g / 10 minutes. When the MFR is in the range of 1 to 10 g / 10 minutes, the stability of heat melt molding is good.

The sheet molding method of the methacrylic resin composition includes an extrusion molding method such as a coextrusion molding method, a T die laminating molding method, and an extrusion coating method; an insert injection molding method, a two-color injection molding method, a core back injection molding method, and a sandwich. Injection molding methods such as an injection molding method and an injection breath molding method; blow molding method; calendar molding method; press molding method; slash molding method and the like can be mentioned.
Generally, for a thin film molded product, the terms "film", "sheet", and "plate" are used depending on the thickness. In the present specification, these are not clearly distinguished, and these are collectively referred to as "sheets".

(Adhesive layer)
The adhesive layer is a transparent layer for adhering a hard resin sheet and a glass plate, and contains a tough soft resin. As the soft resin, polyvinyl butyral, ethylene-vinyl acetate copolymer, ethylene-based ionomer, thermoplastic polyurethane, modified products thereof and the like can be preferably used. The adhesive layer not only has the function of adhering the hard resin sheet and the glass plate, but also reduces the difference in the coefficient of thermal expansion or the difference in the water absorption rate between the hard resin sheet and the glass plate, and is used in durability tests such as heat cycle tests. It is preferable to have a function of suppressing cracking and layer peeling of the glass laminate and a function of improving the impact resistance of the glass laminate. In view of these functions, thermoplastic polyurethane can be particularly preferably used as the soft resin.

Thermoplastic polyurethane is obtained by reacting polyisocyanate with a polyol and a curing agent.
Examples of the polyisocyanate include an aliphatic diisocyanate compound such as hexamethylene diisocyanate, tetramethylene diisocyanate, dodecamethylene diisocyanate, and 2,4,4-trimethyl-1,6-hexanediisocyanate; bis (4-isocyanate cyclohexyl) methane, Alicyclic diisocyanate compounds such as 2,2-bis (4-isocyanatecyclohexyl) propane, 1,4-cyclohexamethylene diisocyanate, and 1-methyl-2,4- (or 2,6) -diisocyanate cyclohexane; isophorone diisocyanate and the like. Examples thereof include an aliphatic / alicyclic mixed diisocyanate compound.

Examples of the polyol include ethylene glycol, 1,3-propanediol, 1,4-butanediol, and 1,6-hexanediol. As the polyol, a polyester diol obtained by subjecting an aliphatic dibasic acid or an anhydride thereof to a dihydric alcohol, preferably an aliphatic dihydric alcohol, to a polyesterization reaction can also be preferably used. Aliphatic dibasic acids can be represented by the formula: HOOC-R-COOH. Here, R in the formula is an alkylene group having 2 to 12 carbon atoms, preferably 4 to 8 carbon atoms, and examples thereof include adipic acid, succinic acid, palmitic acid, suberic acid, azelaic acid, and sebacic acid. The divalent alcohol is preferably an alcohol having 2 to 15 carbon atoms, and specific examples thereof include ethylene glycol, 1,3-propanediol, 1,4-butanediol, and 1,6-hexanediol.

Examples of the polyol include polyoxytetramethylene diol having an oxymethylene group; polyoxyalkylene diol having an oxypropylene group or a combination of an oxyethylene group and an oxypropylene group; an oxyalkylene group such as an oxyethylene group and an oxypropylene group and an oxytetra. Polyether diols having a combination with a methylene group can also be used.

Examples of the curing agent include fatty acid diols such as ethylene glycol, 1,3-propanediol, 1,4-butanediol, and 1,6-hexanediol; amino alcohols such as monoethanolamine; 1,2-ethanediamine. Diamines and the like can be mentioned.

The adhesive layer can be formed by using a thermoplastic polyurethane sheet and a thermoplastic resin sheet such as an ethylene-vinyl acetate copolymer sheet. The thermoplastic resin sheet can be manufactured by a known sheet molding method such as an extrusion molding method.

(Glass plate)
The type of glass plate used in the glass laminate of the present invention is not particularly limited. For example, float glass, polished glass, template glass, braided glass, heat ray absorbing glass, special glass (eg, sputtered metal (eg silver or indium tin oxide) for the purpose of controlling sunlight), low. E glass, tempered glass and the like can be used. These may be colorless or colored. These can be used alone or in combination of two or more.

(Laminated structure)
In the glass laminate of the present invention, the hard resin sheet, the adhesive layer, and the glass plate may be singular or plural, respectively. The glass laminate of the present invention may have layers other than these layers. The constituent materials of the other layers are not particularly limited, and one or more thermoplastic resins excluding the methacrylic resin composition and the soft resin, one or two or more thermosetting resins, one or two or more. Examples include energy ray curable resins and combinations thereof.

The functions of the other resin layers are not particularly limited, and support layers that support hard resin sheets and the like; scratch resistant layers, antistatic layers, antifouling layers, friction reducing layers, antiglare layers, antireflection layers, adhesive layers, heat rays. It may function as various functional layers such as an absorption layer, a sound insulation layer, and an impact strength imparting layer. The other resin layer may be singular or plural. When there are a plurality of other resin layers, the composition may be the same or non-identical.

In one aspect, the rigid resin sheet can have a laminated structure comprising a methacrylic resin composition layer and another thermoplastic resin (composition) layer.
Other thermoplastic resins are not particularly limited, and are, for example, polyolefins such as polyethylene and polypropylene, polystyrene, polyester, polyamide, polycarbonate, polyvinyl chloride, polyvinylidene chloride, polyvinyl alcohol, polyvinylidene fluoride, modified polyphenylene ether, polyphenylene sulfide, and the like. Examples thereof include silicone-modified resins, polyether ether ketones, polysulfones, polyvinylidene oxides, polyimides, polyetherimides, and phenoxy resins. Of these, polycarbonate is preferable from the viewpoint of transparency, heat resistance, and impact resistance.

The thickness of the other plastic resin (composition) layer is preferably 0.04 to 3 mm, more preferably 0.05 to 1.5 mm, and particularly preferably 0.06 to 1.0 mm. preferable. When the thickness of the other plastic resin (composition) layer is 0.04 mm or more, the impact resistance of the glass laminate tends to be excellent, and when it is 3 mm or less, the glass laminate tends to warp. Tends to be suppressed.

In another aspect, the rigid resin sheet can have a laminated structure including a scratch resistant layer and a methacrylic resin composition layer.
The scratch-resistant layer can usually be formed by applying a fluid curable composition containing a monomer, an oligomer, a resin and the like to the surface of another layer (for example, a methacrylic resin composition layer) and curing it. The curable composition is, for example, a thermosetting composition that is cured by heat; an energy ray-curable composition that is cured by energy rays such as electron beam, radiation, and ultraviolet rays.

The thickness of the scratch-resistant layer is preferably 2 to 10 μm, more preferably 3 to 8 μm, and particularly preferably 4 to 7 μm. When the thickness of the scratch-resistant layer is 2 μm or more, the scratch resistance tends to be satisfactorily exhibited, and when the thickness is 10 μm or less, the impact resistance of the glass laminate tends to be excellent.

Examples of the resin contained in the thermosetting composition include phenol resin, urea resin, diallyl phthalate resin, melamine resin, guanamine resin, unsaturated polyester resin, polyurethane resin, epoxy resin, aminoalkyd resin, and melamine-urea cocondensation. Examples thereof include resins, silicon resins, and polysiloxane resins.
The thermosetting composition may contain a curing agent such as a cross-linking agent and a polymerization initiator, a polymerization accelerator or the like, if necessary. As the curing agent, isocyanates and organic sulfonic acids are usually used for polyester resins and polyurethane resins, amines are used for epoxy resins, and peroxides such as methyl ethyl ketone peroxide and azobisisobutyl are used for unsaturated polyester resins. Radical initiators such as esters are used.

Examples of the energy ray-curable composition include a composition containing an oligomer and / or a monomer having a group containing a polymerizable unsaturated bond such as an acryloyl group and a metaacryloyl group, a thiol group, or an epoxy group in the molecule. Be done. From the viewpoint of enhancing scratch resistance, a composition containing an oligomer and / or a monomer having a plurality of acryloyl groups and / or metaacryloyl groups is preferable.

The energy ray-curable composition may contain a photopolymerization initiator and / or a photosensitizer. Photopolymerization initiators include carbonyl compounds such as benzoin methyl ether, acetophenone, 3-methylacetophenone, benzophenone, and 4-chlorobenzophenone; sulfur compounds such as tetramethylthium monosulfide and tetramethylthium disulfide; 2, 4, 6 -Trimethylbenzoyldiphenylphosphine oxide and benzoyldiethoxyphosphine oxide; and the like. Examples of the photosensitizer include n-butylamine, triethylamine, tri-n-butylphosphine and the like.

In the glass laminate of the present invention, the thickness of each layer is not particularly limited.
The thickness of the hard resin sheet is preferably 0.1 to 10 mm, more preferably 0.5 to 5 mm, and particularly preferably 1.0 to 3.0 mm from the viewpoint of scratch resistance, weather resistance, impact resistance, and the like. preferable.
The thickness of the adhesive layer is preferably 0.03 to 8.0 mm, more preferably 0.1 to 7.0 mm, and 0.4 to 6 from the viewpoint of interlayer adhesion, impact resistance, and internal stress relaxation performance. 9.0 mm is particularly preferred.
The thickness of the glass plate is preferably 0.1 to 4.0 mm, more preferably 0.5 to 3.0 mm, and particularly preferably 1.0 to 2.0 mm from the viewpoint of rigidity and weight reduction.

[Manufacturing method of glass laminate]
The method for producing the glass laminate of the present invention is not particularly limited.
For example, a rigid resin sheet manufactured by a known method, a thermoplastic resin sheet for an adhesive layer manufactured by a known method, and a glass plate are laminated, and an autoclave step is performed on the obtained preliminary laminate. Therefore, a glass laminate can be manufactured. The autoclave step is a step of placing the prelaminate in a bag (vacuum bag) that can maintain a vacuum, sucking air from the vacuum bag by a vacuum line or other means, and heating and pressurizing in the autoclave while maintaining the vacuum. Is. The heating temperature and the heating time can be arbitrarily set within the conventionally known ranges. The heating temperature is preferably 120 ° C. or lower, more preferably 110 ° C. or lower so that the hard resin sheet is not thermally deformed.
It should be noted that the at least one surface of the glass plate may be subjected to a known adhesion enhancing treatment in advance prior to the laminating step. Adhesion enhancement treatment is described, for example, in US Pat. No. 7,625,627.

As another manufacturing method, there is a method of obtaining a laminated sheet containing a hard resin sheet and an adhesive layer by a known multilayer molding, and then laminating the obtained laminated sheet to a glass plate. Examples of the multi-layer molding include a laminating synthetic molding method such as multi-layer extrusion molding; multi-layer blow molding; multi-layer press molding; multi-color injection molding; insert injection molding; and the like.

As described above, the glass laminate of the present invention includes a hard resin sheet containing a methacrylic resin composition layer containing a methyl methacrylate (co) polymer and light diffusing particles, an adhesive layer, and a glass plate. ..
Since the glass laminate of the present invention is a composite material containing a hard resin sheet and a glass plate, the weight can be reduced as compared with a single glass. In addition, it is hard to break even if it receives a strong impact from the outside, and even if the glass is broken, the glass fragments do not scatter and it is excellent in safety.
In the glass laminate of the present invention, the hard resin sheet has high heat resistance, and the adhesive layer contains a soft resin. In the glass laminate of the present invention having such a structure, appearance defects and deformation due to heat are suppressed during the laminating process of the hard resin sheet and the glass plate or in an actual use environment, and the layers due to the difference in linear expansion rate between the resin and the glass are suppressed. The peeling of the glass is suppressed. Therefore, according to the present invention, it is possible to provide a high-quality glass laminate having high transparency and excellent durability.
The glass laminate of the present invention is also excellent in light guide performance because the hard resin sheet contains light diffusing particles. By combining the glass laminate of the present invention and a light source, a planar light emitter can be provided. In this planar light emitter, when light is introduced from a light source onto one end surface of the glass laminate, the light is scattered in the thickness direction of the glass laminate and toward the opposite end surface in the surface direction of the glass laminate. Light can be guided well.

[Use]
The use of the glass laminate of the present invention is not particularly limited, and for example, building parts such as safety window glass and partitions; optical light such as liquid crystal protective plate, light guide plate, light guide film, front plate of various displays, and diffuser plate. Related parts; Vehicle parts such as automobile interior / exterior parts (side visor, rear visor, head wing, headlight cover, bumper, sunroof, glazing, etc.); Others, greenhouses, large water tanks, box water tanks, bathroom parts, watch panels, etc. Baths, sanitary, desk mats, game parts, toys, and facial protection masks during welding; etc.
The planar light emitter using the glass laminate of the present invention is suitable as a vehicle member or the like, and is suitable as an automobile glazing material, particularly an automobile sunroof material or the like. By using a planar light emitter using the glass laminate of the present invention, it is possible to provide a high-performance automobile glazing material such as an automobile sunroof material which functions as a transparent plate when the light source is turned off and as an interior lighting when the light source is turned on. It will be possible.

Hereinafter, Examples and Comparative Examples according to the present invention will be described.
[Evaluation items and evaluation methods]
(Evaluation of resin)
<Glass transition temperature (Tg)>
After drying 10 mg of the resin (composition) at 80 ° C. for 24 hours, the resin (composition) was placed in an aluminum pan. After performing nitrogen substitution for 30 minutes or more using a differential scanning calorimeter (“Q20” manufactured by TA Instruments), the temperature is raised from 25 ° C. to 200 ° C. at a rate of 20 ° C./min in a nitrogen stream of 10 ml / min. After holding at 200 ° C. for 10 minutes, the mixture was naturally cooled to 25 ° C. (primary scanning). Then, the temperature was raised to 200 ° C. again at a rate of 10 ° C./min (secondary scanning), and the glass transition temperature (Tg) was calculated by the midpoint method.

<Refractive index and haze>
Using an injection molding machine (SE-180DU-HP manufactured by Sumitomo Heavy Industries, Ltd.), the resin composition is injection molded under the conditions of a cylinder temperature of 280 ° C, a mold temperature of 75 ° C, and a molding cycle of 1 minute. , A square test piece having a thickness of 2 mm and a side of 50 mm was obtained.
The refractive index (nd) of the obtained test piece was measured using an Abbe refractive index meter NAR-3T manufactured by Atago Co., Ltd. in accordance with the method of JIS-K7142 (method A).
The haze of the obtained test piece was measured using a spectrocolorimeter SE5000 manufactured by Nippon Denshoku Industries Co., Ltd. in accordance with the method of JIS-K7361.

(Evaluation of light diffusing particles)
<Average particle size>
An electron micrograph of the primary particles was taken, and the volume-based circle-equivalent diameter was obtained using image analysis type particle size distribution measurement software, and the volume average particle size (μm) was used.

(Evaluation of glass laminate)
<Initial performance>
The presence or absence of layer peeling was evaluated for the glass laminate immediately after production. Those in which each layer was easily peeled off by hand were judged as "with layer peeling", and those in which each layer could not be easily peeled off by hand were judged as "without layer peeling".
In addition, the presence or absence of abnormal appearance was evaluated for the glass laminate immediately after production. Hue (degree of yellowing), optical distortion, and other appearance defects (rough surface of the outermost layer, wrinkles, bubbles, and whitening of the intermediate layer, etc.) are visually confirmed as "appearance defects". Those in which no abnormality was confirmed were judged to have "good appearance".

<Durability>
The manufactured glass laminate was left in an environment of humidity 20% and temperature 20 ° C. for 1 hour, left in an environment of humidity 20% and temperature 80 ° C. for 1 hour, and left in an environment of humidity 100% and temperature 20 ° C. It was left for 1 hour in an environment with a humidity of 100% and a temperature of 80 ° C. for 1 hour. The above operation was set as one cycle, and 100 cycles were repeated. After performing this heat cycle test, the presence or absence of layer peeling and the appearance of the glass laminate of the laminate were evaluated by the same method as the initial performance.

<Scratch resistance>
The surface pencil scratch hardness of the manufactured glass laminate was measured using a table-movable pencil scratch tester (model P, manufactured by Toyo Seiki Co., Ltd.). The surface to be evaluated was the surface of the hard resin sheet shown in Table 3.
Under the conditions of an angle of 45 degrees and a load of 750 g, the pencil core was pressed against the surface of the glass laminate and scratched, and the presence or absence of scratches was confirmed. The hardness of the pencil lead increased in order, and the hardness of the lead, which was one step softer than the time when the scar was generated, was used as the scratch resistance data.
Further, the surface of the manufactured glass laminate was measured for the Taber wear resistance performance using a Taber type wear tester (AB-101) (manufactured by Tester Sangyo Co., Ltd.). The surface to be evaluated was the surface of the hard resin sheet shown in Table 3. The measurement was performed according to the method of ASTM D-1044. The wear ring was CS-10F, the load was 500 g, and the rotation speed was 1000 times. The difference in haze (ΔH (%)) before and after the Tabor wear test was measured. The smaller ΔH (%), the better the tabor wear performance.
When the pencil hardness is 2H or more and the haze difference (ΔH) before and after the Taber wear test is 10% or less, the scratch resistance is good (○), the pencil hardness is H or less, or before and after the Taber wear test. When the difference in haze (ΔH) was larger than 10%, it was determined that the scratch resistance was poor (x).

(Evaluation of planar illuminant)
A planar illuminant was prepared and evaluated using the manufactured glass laminate.
FIG. 5 shows a schematic cross-sectional view of the evaluation system.
The planar light emitter 50 shown in FIG. 5 includes a light source 51 and a glass laminate 52.
The glass laminate 52 was previously subjected to a known light absorption treatment 54 on the other end surface 52B facing the end surface 52A on the light incident side. A light source 51 and a light reflection cover 55 are arranged adjacent to the end surface 52A on the light incident side of the glass laminate 52. As the light source 51, seven LEDs arranged in a row in a direction parallel to the end face on the light incident side of the glass laminate at intervals of 10 mm were used. As the LED, "LED NFSW036BT" manufactured by Nichia Corporation (diameter of light emitting portion: 3 mm) was used. A voltage of 2.8 V was applied to each LED. On the back surface side of the planar light emitter 50, a light absorption sheet 53 for absorbing the light emitted to the back surface side was arranged.
The light emitted from the light source 51 is incident from the end surface 52A on the light incident side of the glass laminate 52, and is guided through the inside of the glass laminate 52 toward the other end surface 52B to which the light absorption treatment 54 is applied. The distance from the end face 52A on the light incident side to the other end face 52B to which the light absorption treatment 54 was applied was set to 300 mm. The position of the end face 52A on the light incident side was set to 0 mm, and the distance to an arbitrary point up to the other end face 52B to which the light absorption treatment 54 was applied was defined as the "light guide distance".

<Transparency>
With the light source turned off, the transparency of the planar illuminant is visually evaluated, and from the one with the lowest transparency to the one with the highest transparency, 5 of "1", "2", "3", "4", and "5". Evaluated in stages. In addition, "4" or more was judged as "good".

<Brightness>
With the light source turned on, the brightness was visually evaluated at the positions where the distance from the light source (light guide distance) was 50 mm and 150 mm. The evaluation was made on a five-point scale of "1", "2", "3", "4", and "5" from the one with the lowest brightness to the one with the highest brightness. In addition, "4" or more was judged as "good".

<Color unevenness>
With the light source turned on, the degree of change in color from the end face on the light incident side at positions where the distance from the light source (light guide distance) was 50 mm and 150 mm was visually evaluated. Evaluation was made on a five-point scale of "1", "2", "3", "4", and "5" from the one with a large change in color from the end face on the light incident side to the one with a small change. In addition, "4" or more was judged as "good".

[material]
<Methyl methacrylate homopolymer (A-1)>
A parapet manufactured by Kuraray Co., Ltd. (methyl methacrylate homopolymer (MMA ratio = 100%), Mw = 82,000, rr ratio = 52%) was used as the methyl methacrylate homopolymer (A-1).

<Methyl methacrylate homopolymer (A-2)>
The inside of the autoclave equipped with a stirrer and a sampling tube was replaced with nitrogen. To this, 100 parts by mass of purified methyl methacrylate (MMA), 2,2'-azobis (2-methylpropionitrile (hydrogen extraction capacity: 1%, 1 hour half-life temperature: 83 ° C.) 0.0065% by mass. Parts and 0.290 parts by mass of n-octyl mercaptan were added and stirred to obtain a raw material solution. Nitrogen was sent into the raw material solution to remove dissolved oxygen in the raw material solution.
The raw material liquid was put into a tank reactor connected to the autoclave by piping up to 2/3 of the capacity. The temperature was maintained at 120 ° C., and the polymerization reaction was first started by a batch method. When the polymerization conversion rate reaches 55% by mass, the raw material liquid is supplied from the autoclave to the tank reactor at a flow rate with an average residence time of 120 minutes while maintaining the temperature at 120 ° C., and the raw material liquid supply flow rate. The reaction solution was withdrawn from the tank reactor at a flow rate corresponding to that of the above, and the polymerization reaction was switched to the continuous flow method. After switching, the polymerization conversion rate in the steady state was 45% by mass.
The reaction solution extracted from the tank-type reactor in a steady state was supplied to a multi-tube heat exchanger having an internal temperature of 230 ° C. at a flow rate having an average residence time of 2 minutes and heated. Then, the heated reaction solution was introduced into a flash evaporator, and the volatile matter containing the unreacted monomer as a main component was removed to obtain a molten resin. The molten resin from which the volatile components have been removed is supplied to a twin-screw extruder having an internal temperature of 230 ° C., discharged in a strand shape, cut with a pelletizer, and pellet-shaped with Mw = 83,000 and an rr ratio = 54%. A methyl methacrylate homopolymer (A-2) (MMA ratio = 100%) was obtained.

<Methyl methacrylate homopolymer (A-3)>
The inside of the autoclave equipped with a stirrer and a sampling tube was replaced with nitrogen. To this, 100 parts by mass of purified methyl methacrylate (MMA), 2,2'-azobis (2-methylpropionitrile (hydrogen extraction capacity: 1%, 1 hour half-life temperature: 83 ° C.) 0.0094% by mass. Parts and 0.26 parts by mass of n-octyl mercaptan were added and stirred to obtain a raw material solution. Nitrogen was sent into the raw material solution to remove dissolved oxygen in the raw material solution.
The raw material liquid was put into a tank reactor connected to the autoclave by piping up to 2/3 of the capacity. The temperature was maintained at 100 ° C., and the polymerization reaction was first started by a batch method. When the polymerization conversion rate reached 42% by mass, the temperature was maintained at 120 ° C., and the raw material liquid was supplied from the autoclave to the tank reactor at a flow rate with an average residence time of 120 minutes, and the supply flow rate of the raw material liquid was adjusted. At a corresponding flow rate, the reaction solution was withdrawn from the tank reactor and switched to a continuous flow polymerization reaction. After switching, the polymerization conversion rate in the steady state was 49% by mass.
The reaction solution extracted from the tank-type reactor in a steady state was supplied to a multi-tube heat exchanger having an internal temperature of 230 ° C. at a flow rate having an average residence time of 2 minutes and heated. Then, the heated reaction solution was introduced into a flash evaporator, and the volatile matter containing the unreacted monomer as a main component was removed to obtain a molten resin. The molten resin from which the volatile components have been removed is supplied to a twin-screw extruder having an internal temperature of 230 ° C., discharged into a strand shape, cut with a pelletizer, and pellet-shaped with Mw = 92,000 and an rr ratio = 56%. A methyl methacrylate homopolymer (A-3) (MMA ratio = 100%) was obtained.

<Methyl methacrylate homopolymer (A-4)>
The inside of a 5 L glass reaction vessel equipped with a stirring blade and a three-way cock was replaced with nitrogen. To this, at room temperature, 1600 g of toluene, 2.49 g (10.8 mmol) of 1,1,4,7,10,10-hexamethyltriethylenetetramine, and isobutylbis (2,6-di) having a concentration of 0.45 M. 6. Toluene solution 53.5 g (30.9 mmol) of -t-butyl-4-methylphenoxy) aluminum and sec-butyllithium solution at a concentration of 1.3 M (solvent: cyclohexane 95%, n-hexane 5%) 6. 17 g (10.3 mmol) was charged. While stirring, 550 g of distilled and purified methyl methacrylate (MMA) was added dropwise at 20 ° C. over 30 minutes. After completion of the dropping, the mixture was stirred at 20 ° C. for 90 minutes. The color of the solution changed from yellow to colorless. At this point, the polymerization conversion rate of MMA was 100%.
1500 g of toluene was added to the obtained solution to dilute it. Then, the diluted solution was poured into 100 kg of methanol to obtain a precipitate. The obtained precipitate was dried at 80 ° C. and 140 Pa for 24 hours to obtain a methyl methacrylate homopolymer (A-4) (MMA ratio = 100%) having Mw = 81400 and an rr ratio = 73%. ..

<Methyl methacrylate copolymer (A-5)>
The inside of a 5 L glass reaction vessel equipped with a stirring blade and a three-way cock was replaced with nitrogen. To this, 630 g of methyl methacrylate (MMA), 350 g of tricyclo [5.2.1.0 ^2,6 ] decanyl (TCDMA), 20 g of methyl acrylate (MA), and azobisisobutyronitrile were added. 0.6 g, 2.0 g of n-octyl mercaptan, 2500 g of ion-exchanged water, 0.9 g of a dispersant, and 10.7 g of a pH adjuster were charged. While stirring, the liquid temperature was raised from room temperature to 70 ° C. and held for 120 minutes to carry out the polymerization reaction. Then, the liquid temperature was lowered to room temperature, and the polymerization reaction liquid was withdrawn from the glass reaction vessel. The polymerization reaction solution was filtered to remove the solid content, washed with water, and dried with hot air at 80 ° C. for 24 hours. The obtained solid content was supplied to the hopper of the twin-screw extruder and melt-kneaded at a cylinder temperature of 230 ° C. Then, the molten resin is extruded to obtain a pellet-shaped methyl methacrylate copolymer (A) having an MMA ratio of 67.2%, a TCDMA ratio of 31.7%, an MA ratio of 1.1%, and Mw = 119,300. -5) was obtained.

<Methyl methacrylate copolymer (A-6)>
A parapet manufactured by Kuraray Co., Ltd. (MMA ratio = 93.6%, MA ratio = 6.4%, Mw = 120,000, rr ratio = 48%) was used as the methyl methacrylate copolymer (A-6).

<Methyl methacrylate copolymer (B-1)>
"Regisphy R-200" manufactured by Denki Kagaku Kogyo Co., Ltd. (styrene / maleic anhydride / MMA = 56% / 18% / 26%, Mw = 80,000) is used as a methyl methacrylate copolymer (B-1). board.

<Polycarbonate resin (PC-1)>
"Calibre 300-8" manufactured by Sumika Stylon Polycarbonate Co., Ltd. (Mw = 50,000, temperature 300 ° C., MFR = 6.7 g / 10 minutes under 1.2 kg load) was used as the polycarbonate (PC-1). ..

<Light diffusion particles (a-1)>
TAYCA Corporation Titanium oxide "TITANIX JR-1000" (average particle diameter = 1.0 μm, refractive index = 2.72) was used as the light diffusing particles (a-1).
<Light diffusion particles (a-2)>
Cross-linked polystyrene beads "Fine Pearl" (average particle size = 3.0 μm, refractive index = 1.58) manufactured by Matsuura Co., Ltd. were used as light diffusing particles (a-2).

<Bluing agent (b-1)>
Mitsubishi Chemical Corporation "Dialesin Blue N" was used as a bluing agent (b-1).
<Bluing agent (b-2)>
Mitsubishi Chemical Corporation "Dialesin Blue G" was used as a bluing agent (b-2).

<UV absorber>
"ADEKA STAB LA-46" manufactured by ADEKA Corporation was used as an ultraviolet absorber.

<Thermoplastic polyurethane sheet>
"Hygress DUS203" manufactured by Seadam Co., Ltd. (polyester-based thermoplastic polyurethane containing aromatic diisocyanate and polyester diol as main reaction components, thickness 500 μm) was used as the thermoplastic polyurethane sheet.

<Ethylene-vinyl acetate copolymer sheet>
"Ultrasen 634" manufactured by Tosoh Corporation (vinyl acetate content = 26% by mass, temperature 190 ° C., MFR under load of 21.18N = 4.3g / 10 minutes, thickness 500μm) with ethylene-vinyl acetate It was used as a polymer sheet.

[Manufacturing Examples 1-1 to 1-11]
Methyl methacrylate (co) polymer (A-1) to (A-6), methyl methacrylate copolymer (B), light diffusing particles (a-) in the compounding ratios shown in Table 1-1 and Table 1-2. 1)-(a-2), brewing agents (b-1)-(b-2), and ultraviolet absorbers are supplied to the hopper of the twin-screw extruder, melt-kneaded at a cylinder temperature of 240 ° C., and extruded. Molding was performed to obtain pellet-shaped methacrylic resin compositions (1) to (11). The composition and physical properties of these methacrylic resin compositions are shown in Table 1-1 and Table 1-2.

[Manufacturing Example 1-12]
Polycarbonate resin (PC-1), light diffusing particles (a-1), and an ultraviolet absorber were supplied to the hopper of the twin-screw extruder at the blending ratios shown in Table 1, and melt-kneaded at a cylinder temperature of 250 ° C. Extrusion molding was performed to obtain a pellet-shaped polycarbonate resin composition (12). The composition and physical properties of this polycarbonate resin composition are shown in Table 1-2.

[Manufacturing Examples 2-1 to 2-7, 2-10 to 2-14]
Hard resin sheets (1) to (7) and (10) to (14) were produced using the methacrylic resin compositions (1) to (7) and (10) to (14) by the following methods. ..
Pellets of the methacrylic resin composition shown in Table 2 were continuously charged into a vent-type single-screw extruder having a shaft diameter of 50 mm, and melt-extruded under the conditions of a cylinder temperature of 190 to 250 ° C. and a discharge rate of 30 kg / hour. Next, the molten methacrylic resin composition was extruded from a T-die having a width of 400 mm set at 250 ° C. and niped with a pair of metal rigid body rolls set at 100 ° C. and 120 ° C. to form a sheet. It was picked up at a speed of 47 m / min. As described above, a methacrylic resin sheet having a width of 300 mm, a length of 400 mm, and a thickness of 2 mm was obtained.
In Production Examples 2-1 to 2-7 and 2-11 to 2-14, an ultraviolet curable hard coat paint containing a polyfunctional acrylic resin on one surface of the methacrylic resin sheet obtained by the above method (Japan). A scratch-resistant layer (about 4 μm) was formed by a roll-coating method using UV-1700B) manufactured by Nippon Synthetic Chemical Industry Co., Ltd. to obtain a hard resin sheet with a scratch-resistant layer.
In Production Example 2-10, the methacrylic resin sheet obtained by the above method was used as a hard resin sheet without forming a scratch resistant layer.
Table 2 shows the structure of the hard resin sheet obtained in each production example.

[Manufacturing Examples 2-8 to 2-9]
The pellets of the methacrylic resin composition (1) were continuously charged into a vent-type single-screw extruder having a shaft diameter of 50 mm, and melt-extruded under the conditions of a cylinder temperature of 190 to 250 ° C. and a discharge rate of 24 kg / hour. Pellets of the methacrylic resin composition (6) or the polycarbonate resin composition (12) are continuously charged into a vent-type single-screw extruder having a shaft diameter of 30 mm, and the cylinder temperature is 190 to 300 ° C. and the discharge rate is 6 kg / hour. Was melt-extruded.
The melted methacrylic resin composition (1) and the methacrylic resin composition (6) or the polycarbonate resin composition (12) are introduced into a junction block and laminated by a multi-manifold die having a width of 400 mm set at 250 ° C. It was extruded (co-extruded) and niped with a pair of rigid metal rolls set at 100 ° C. and 120 ° C. to form a sheet, which was taken up at a speed of 0.47 m / min.
As described above, the first resin layer (thickness 1.6 mm) made of the methacrylic resin composition (1) and the second resin made of the methacrylic resin composition (6) or the polycarbonate resin composition (12). A laminated resin sheet (width 300 mm, length 400 mm, thickness 2 mm) having a two-layer structure in which layers (thickness 0.4 mm) were laminated was obtained.
A scratch-resistant layer (about 4 μm) was formed on the surface of the first resin layer of the obtained laminated resin sheet in the same manner as in Production Example 2-1 to obtain a hard resin sheet with a scratch-resistant layer. Table 2 shows the structure of the hard resin sheet obtained in each production example.

[Manufacturing Example 2-15]
The pellets of the polycarbonate resin composition (12) were continuously charged into a vent-type single-screw extruder having a shaft diameter of 50 mm, and melt-extruded under the conditions of a cylinder temperature of 190 to 300 ° C. and a discharge rate of 30 kg / hour. Next, the molten polycarbonate resin composition (12) was extruded from a T-die having a width of 400 mm set at 270 ° C. and niped with a pair of metal rigid body rolls set at 100 ° C. and 120 ° C. to form a sheet. , 0.47 m / min. As described above, a polycarbonate resin sheet having a width of 300 mm, a length of 400 mm, and a thickness of 2 mm was obtained. A scratch-resistant layer (about 4 μm) was formed on one surface of the obtained polycarbonate resin sheet in the same manner as in Production Example 2-1 to obtain a hard resin sheet with a scratch-resistant layer. The structure of the obtained hard resin sheet is shown in Table 2.

[Examples 1 to 7, 9 to 11]
A thermoplastic polyurethane sheet as an adhesive layer and a commercially available float glass plate (G1) (thickness 2.8 mm) were sequentially laminated on the hard resin sheet shown in Table 3. When a hard resin sheet containing a scratch-resistant layer was used, an adhesive layer was laminated on the non-formed surface of the scratch-resistant layer of the hard resin sheet. The obtained preliminary laminate was heated by a vacuum bag method (temperature profile: heated from 30 ° C. to 110 ° C. for 60 minutes and then held at 110 ° C. for 30 minutes) and pressurized to prepare a glass laminate. Tables 3 and 4 show the structures and evaluation results of the glass laminates produced in each example.

[Example 8]
A glass laminate was prepared in the same manner as in Example 7 except that an ethylene-vinyl acetate copolymer (EVA) sheet was used instead of the thermoplastic polyurethane sheet. Tables 3 and 4 show the structure and evaluation results of the glass laminate produced in Example 8.

[Comparative Examples 1 to 5]
A glass laminate was produced in the same manner as in Example 1 except that the hard resin sheet shown in Table 3 was used. Tables 3 and 4 show the structures and evaluation results of the glass laminates produced in Comparative Examples 1 to 5.

[Summary of evaluation results]
In Examples 1 to 11, a rigid resin sheet containing a methyl methacrylate (co) polymer and light diffusing particles and having a glass transition temperature (Tg) of 120 ° C. or higher and containing a methacrylic resin composition layer, and a thermoplastic polyurethane A glass laminate having a three-layer structure of an adhesive layer made of a sheet or an ethylene-vinyl acetate copolymer sheet and a glass plate was obtained.
None of the glass laminates obtained in Examples 1 to 11 using the hard resin sheet containing the highly heat-resistant methacrylic resin composition layer caused layer peeling and appearance defects immediately after production and after the heat cycle test. , Transparency and durability were good. By using the glass laminates of Examples 1 to 11 using a hard resin sheet containing a methacrylic resin composition layer containing an appropriate amount of appropriate light diffusing particles, transparency is good when the light source is turned off, and light is obtained when the light source is turned on. It was possible to produce a planar light source having good emission and excellent surface emission.
In Examples 1 to 11, two types of light diffusing particles having different refractive indexes and average particle sizes were used. The larger the difference in refractive index between the matrix resin of the methacrylic resin composition and the light diffusing particles, the better the light emission property when the light source is lit. The larger the particle size of the light diffusing particles, the better the light emission property when the light source is lit. The smaller the particle size of the light diffusing particles, the better the transparency when the light source was turned off.

In the glass laminates obtained in Comparative Examples 1 to 3 using the hard resin sheets (11) to (13) containing the methacrylic resin composition layer having low heat resistance, the layer was peeled off or the surface was roughened immediately after production or after the heat cycle test. There has occurred. The planar illuminant using the glass laminate of Comparative Example 4 using the hard resin sheet (14) containing the methacrylic resin composition layer containing no light diffusing particles had insufficient brightness when the light source was turned on. .. Further, the glass laminate obtained in Comparative Example 5 using the hard resin sheet (15) containing the polycarbonate resin composition layer causes optical strain immediately after production and after the heat cycle test, and has insufficient scratch resistance. there were. Further, in the planar light emitter using the glass laminate of Comparative Example 5, the transparency was insufficient when the light source was turned off, the brightness was insufficient when the light source was turned on, and color unevenness was observed.

The present invention is not limited to the above embodiments and examples, and the design can be appropriately changed as long as the gist of the present invention is not deviated.

This application claims priority on the basis of Japanese Application Japanese Patent Application No. 2016-202993 filed on October 14, 2016 and incorporates all of its disclosures herein.

R1, R2 Rigid resin sheet 11 Methacrylic resin composition layer 12 Adhesive layer 13 Glass plate 14 Other thermoplastic resin (composition) layer 21 Scratch resistant layer 10X, 10Y, 20X, 20Y Glass laminate 50 Planar light source 51 Light source 52 Glass laminate 53 Light absorption sheet 54 Light absorption treatment 55 Light reflection cover

Claims (14)

A laminate having a glass plate arranged via an adhesive layer on one surface of a hard resin sheet.
The hard resin sheet contains a layer made of a methacrylic resin composition containing a methyl methacrylate (co) polymer and light diffusing particles and having a glass transition temperature of 120 ° C. or higher.
The methacrylic resin composition contains 0.00005 to 0.1% by mass of the light diffusing particles.
The absolute value of the refractive index difference (Δn) between the refractive index of the matrix resin of the methacrylic resin composition and the refractive index of the light diffusing particles is 0.3 to 3.
The product of the absolute value of the refractive index difference (Δn) and the volume average particle diameter d (μm) of the light diffusing particles is 0.1 μm or more.
A laminate in which the soft resin constituting the adhesive layer is thermoplastic polyurethane . The methyl methacrylate (co) polymer (A) is a methyl methacrylate (co) polymer composed of 60 to 100% by mass of the methyl methacrylate unit and 40 to 0% by mass of the (meth) acrylic acid ester unit other than methyl methacrylate. The laminate according to claim 1. The laminate according to claim 2, wherein the methyl methacrylate (co) polymer (A) has a syndiotacticity (rr) of 58 to 85% in triplet representation. The methyl methacrylate (co) polymer is a methyl methacrylate copolymer composed of 10 to 35% by mass of the methyl methacrylate unit, 15 to 40% by mass of the maleic anhydride unit, and 50 to 75% by mass of the aromatic vinyl compound unit. The laminate according to claim 1, which comprises (B). The methacrylic resin composition
5 to 80% by mass of the methyl methacrylate (co) polymer (A) consisting of 60 to 100% by mass of the methyl methacrylate unit and 40 to 0% by mass of the (meth) acrylic acid ester unit other than methyl methacrylate, and
Claimed to contain 95 to 20% by mass of the methyl methacrylate copolymer (B) consisting of 10 to 35% by mass of the methyl methacrylate unit, 15 to 40% by mass of the maleic anhydride unit and 50 to 75% by mass of the aromatic vinyl compound unit. The laminate according to any one of 1 to 4. The laminate according to any one of claims 1 to 5 , wherein the light diffusing particles include titanium oxide particles . The laminate according to any one of claims 1 to 6 , wherein the methacrylic resin composition contains 0.0001 to 0.01% by mass of a bluing agent. The hard resin sheet is a laminated sheet including a layer made of the methacrylic resin composition and a layer made of another thermoplastic resin.
The laminate according to any one of claims 1 to 7 , wherein the laminate has the adhesive layer on the surface of a layer made of the other thermoplastic resin. The laminate according to any one of claims 1 to 8 , further comprising a scratch resistant layer on the other surface of the rigid resin sheet of the laminate. A vehicle member including the laminate according to any one of claims 1 to 9 . An automobile glazing material containing the laminate according to any one of claims 1 to 9 . An automobile sunroof material containing the laminate according to any one of claims 1 to 9 . A light guide plate including the laminate according to any one of claims 1 to 9. A planar light emitter comprising the laminate according to any one of claims 1 to 9.

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