JP2021030668A - Methacrylic resin laminate and application thereof - Google Patents

Abstract

To provide a methacrylic resin laminate which has scattering prevention properties in a wide temperature region including a low temperature region while having transparency and rigidity inherent to the methacrylic resin.SOLUTION: A methacrylic resin laminate (10) has a laminate structure in which first resin layers (11) containing a methacrylic resin (A) are laminated on both surfaces of a second resin layer (12) containing a thermoplastic elastomer (B) that is a block copolymer including a polymer block (b-1) containing an aromatic vinyl monomer unit and a polymer block (b-2) including a conjugated diene monomer unit or its hydrogenated product. When dynamic viscoelasticity measurement is performed according to JIS-K-7244-4 on the condition of a frequency of 1.0 Hz and data of a change of a loss tangent (tanδ) to the temperature is acquired, the thermoplastic elastomer (B) has at least one loss tangent (tanδ) peak in a temperature range of -60 to -30°C.SELECTED DRAWING: Figure 1

Description

The present invention relates to a methacrylic resin laminate containing a first resin layer containing a methacrylic resin and a second resin layer containing a thermoplastic elastomer, and uses thereof.

As applications of transparent resin plates (hereinafter, also referred to as shatterproof plates) that are required to prevent debris from scattering when impacted, windows for vehicles and glazing for moving objects such as canopies; machine tools and their viewing windows. Machine tools that protect such as sound insulation plates and protective plates used in highways and high-speed railways. Conventionally, a polycarbonate-based resin plate has been widely used as a transparent resin plate for such applications, but its weather resistance and abrasion resistance are not sufficient.

Patent Document 1 discloses a shatterproof plate which is made of an acrylic resin plate in which a single fiber plastic filament is embedded and is suitable as a soundproof wall (claim 1).
Patent Document 2 discloses a transparent shatterproof plate in which acrylic resin layers are laminated on both sides of a soft acrylic resin layer (claim 1).
Patent Documents 3 to 5 disclose a transparent shatterproof plate using a styrene-based thermoplastic elastomer having excellent viscoelastic properties. Patent Document 3 discloses an interlayer film for laminated glass containing a sound insulating layer containing a styrene-based thermoplastic elastomer, and a laminated glass using the same (claims 1, 5 to 7, 14, paragraph 0038, etc.). ). Patent Document 4 describes a laminate including a base material layer containing a (meth) acrylic resin and an adhesive layer containing a styrene-based thermoplastic elastomer containing an aromatic vinyl polymer block and a conjugated diene polymer block. Are disclosed (claims 1, 10, paragraphs 0026, 0037, 0041, etc.). Patent Document 5 discloses a laminate containing a first resin layer containing a methacrylic resin, a second resin layer containing a styrene-based thermoplastic elastomer, and a third resin layer containing an ionomer (claim). Item 1).

International Publication No. 2000/20690 Japanese Unexamined Patent Publication No. 2013-116589 International Publication No. 2016/07640 International Publication No. 2017/200014 International Publication No. 2017/191826

The shatterproof plate described in Patent Document 1 has poor transparency because a single fiber plastic filament is embedded in the acrylic resin plate.
The shatterproof plate described in Patent Document 2 does not have good viscoelastic properties of the soft acrylic resin at low temperatures, so that sufficient shatterproof properties cannot be obtained at low temperatures.
Patent Documents 3 to 5 do not describe the anti-scattering property at low temperatures and are unclear.
Conventionally, no transparent resin plate having excellent anti-scattering property has been reported in a wide temperature range including a low temperature range. As used herein, the term "low temperature" refers to, for example, a temperature of −60 to −30 ° C.

The present invention has been made in view of the above circumstances, and provides a methacrylic resin laminate having anti-scattering properties in a wide temperature range including a low temperature range while maintaining the original transparency and rigidity of the methacrylic resin. The purpose is to do.

The present invention provides the following methacrylic resin laminates [1] to [11] and their uses.
[1] The first resin layer containing the methacrylic resin (A) is a polymer block (b-1) containing an aromatic vinyl monomer unit and a polymer block (b-) containing a conjugated diene monomer unit. It has a laminated structure laminated on both sides of a block copolymer containing 2) and a second resin layer containing a thermoplastic elastomer (B) which is a hydrogenated additive of the block copolymer.
When the thermoplastic elastomer (B) was subjected to dynamic viscoelasticity measurement under the condition of a frequency of 1.0 Hz in accordance with JIS-K7244-4 and the data of the change in loss tangent (tan δ) with respect to temperature was acquired, the data was obtained. A methacrylic resin laminate having at least one loss tangent (tan δ) peak in the temperature range of −60 to −30 ° C.

[2] The polymer block (b-1) is a methacrylic resin laminate according to [1], which contains an α-methylstyrene monomer unit as the aromatic vinyl monomer unit.
[3] When an impact test is carried out under the conditions of an environmental temperature of -40 ° C and an impact fracture energy value of 0.245 J in accordance with JIS-K7211-1, the number of fragments separated from the methacrylic resin laminate is The methacrylic resin laminate of [1] or [2], which is 0.
[4] The first resin layer is any one of [1] to [3], which contains 95 to 60% by mass of the methacrylic resin (A) and 5 to 40% by mass of the multilayer structure rubber particles (C). Methacrylic resin laminate.

[5] The methacrylic according to any one of [1] to [4], wherein the second resin layer contains 95 to 60% by mass of the thermoplastic elastomer (B) and 5 to 40% by mass of the methacrylic resin (D). Based resin laminate.
[6] The methacrylic resin (D) has a weight average molecular weight of 80,000 or less, and contains 80% by mass or more of methyl methacrylate monomer unit and 5% by mass or more of methyl acrylate monomer unit. 5] methacrylic resin laminate.
[7] The methacrylic resin laminate according to any one of [1] to [6], wherein the ratio of the total thickness of the first resin layer to the total thickness is 50% or more.
[8] The methacrylic resin laminate according to any one of [1] to [7], which has a flexural modulus of 1500 MPa or more.

[9] Glazing for a mobile body, which comprises the methacrylic resin laminate according to any one of [1] to [8].
[10] A machine cover containing the methacrylic resin laminate according to any one of [1] to [8].
[11] A translucent sound insulating plate containing the methacrylic resin laminate according to any one of [1] to [8].

According to the present invention, it is possible to provide a methacrylic resin laminate having anti-scattering properties in a wide temperature range including a low temperature range while maintaining the transparency and rigidity inherent in the methacrylic resin.

It is a schematic cross-sectional view of the methacrylic resin laminate of one Embodiment which concerns on this invention.

Hereinafter, the present invention will be described in detail.
"Methacrylic resin laminate"
In the methacrylic resin laminate of the present invention, the first resin layer containing the methacrylic resin (A) contains a polymer block (b-1) containing an aromatic vinyl monomer unit and a conjugated diene monomer unit. A laminated structure laminated on both sides of a block copolymer containing the polymer block (b-2) containing the block copolymer or a second resin layer containing the thermoplastic elastomer (B) which is a hydrogenated additive of the block copolymer. Have.
The thermoplastic elastomer (B) was subjected to dynamic viscoelasticity measurement under the condition of a frequency of 1.0 Hz in accordance with JIS-K7244-4, and the data (tanδ curve) of the change in loss tangent (tanδ) with respect to temperature was obtained. When obtained, it is a resin having at least one loss tangent (tan δ) peak in the temperature range of −60 to −30 ° C.
The first resin layer preferably contains a methacrylic resin (A) and multi-layered rubber particles (C). The second resin layer preferably contains a thermoplastic elastomer (B) and a methacrylic resin (D).
Hereinafter, the "methacrylic resin laminate" may be simply abbreviated as "laminate".

FIG. 1 shows a schematic cross-sectional view of a methacrylic resin laminate according to an embodiment of the present invention. In the figure, reference numeral 10 indicates a laminate of the present embodiment, reference numeral 11 indicates a first resin layer containing a methacrylic resin, and reference numeral 12 indicates a second resin layer containing a thermoplastic elastomer (B). The laminated body 10 of the illustrated example is a laminated body having a three-layer structure composed of two first resin layers 11 and one second resin layer 12. The methacrylic resin laminate of the present invention is not limited to the three-layer structure, and may include any other one or more layers, if necessary.

The methacrylic resin laminate of the present invention contains a plurality of polymer blocks having a specific structure, and has at least one loss tangent (tan δ) in a low temperature region, specifically, a temperature region of -60 to -30 ° C. It has a laminated structure in which the first resin layer containing the methacrylic resin (A) is laminated on both sides of the second resin layer containing the thermoplastic elastomer (B) having a peak.

Since the laminate of the present invention contains a second resin layer containing a thermoplastic elastomer (B) having good viscoelastic properties at low temperatures as an inner layer, it has a wide temperature range including low temperature and normal temperature (for example, −60 to 30 ° C.). ), It is possible to have good anti-scattering properties.
According to the present invention, it is possible to provide a laminate having no or less prevention of scattering of fragments when subjected to an impact in a wide temperature range including low temperature and room temperature. According to the present invention, for example, when an impact test is carried out under the conditions of an environmental temperature of −40 ° C. and an impact fracture energy value of 0.245 J in accordance with JIS-K7211-1, the resin is separated from the methacrylic resin laminate. It is possible to provide a methacrylic resin laminate having 0 debris. The laminated body of the present invention is highly safe for the human body, and can be suitably used as a glazing for a moving body, a machine cover, a translucent sound insulating plate, and the like.

Since the laminate of the present invention does not use a single fiber plastic filament, it can exhibit anti-scattering properties while having good transparency.
Since the laminate of the present invention has two first resin layers containing a methacrylic resin (A) sandwiching a second resin layer containing a thermoplastic elastomer (B), the transparency inherent in the methacrylic resin is inherent. It can have characteristics such as property and rigidity as it is. When the first resin layer contains the multilayer structure rubber particles (C), the laminate of the present invention is also excellent in impact resistance and is preferable.

(First resin layer)
<Methacrylic resin (A)>
The first resin layer contains one or more methacrylic resins (A). The transparency of the first resin layer tends to improve and the surface hardness tends to increase as the content of the methacrylic resin (A) increases. The content of the methacrylic resin (A) in the first resin layer is not particularly limited, and is preferably 60% by mass or more, more preferably 70% by mass, from the viewpoint of transparency and surface hardness of the first resin layer. As mentioned above, it is particularly preferably 80% by mass or more.

The methacrylic resin (A) is polymethyl methacrylate (PMMA), which is a homopolymer of methyl methacrylate (MMA), or a copolymer of MMA and one or more other monomers. is there. The content of the MMA monomer unit in the methacrylic resin (A) is not particularly limited, and is preferably 80% by mass or more, more preferably 90% by mass or more, and further, from the viewpoint of heat resistance of the first resin layer. It is preferably 95% 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 copolymer is determined by purifying the copolymer by reprecipitation in methanol, and then performing thermal decomposition and separation of volatile components using pyrolysis gas chromatography to obtain MMA. It can be calculated from the ratio of the peak area to the copolymerization component.

Examples of the monomer copolymerizable with MMA include methacrylic acid esters other than MMA. Specifically, alkyl methacrylate esters such as ethyl methacrylate, n-propyl methacrylate, isopropyl methacrylate, n-butyl methacrylate, isobutyl methacrylate, and tert-butyl methacrylate; and 1-methylcyclopentyl methacrylate and the like. Examples thereof include cycloalkyl esters of methacrylic acid; arylacrylates of methacrylic acid such as phenyl methacrylate; and aralkyl esters of methacrylic acid such as benzyl methacrylate.

Examples of monomers other than the methacrylate ester that can be copolymerized with MMA include methyl acrylate (MA), ethyl acrylate, n-propyl acrylate, isopropyl acrylate, n-butyl acrylate (BA), and isobutyl acrylate. , And acrylic acid esters such as tert-butyl acrylate.

The weight average molecular weight (Mw) of the methacrylic resin (A) is not particularly limited, and is preferably 30,000 to 500,000, more preferably 40,000 to 500,000, and particularly preferably 60,000 to 300,000. , Most preferably 80,000-200,000. When Mw is 30,000 or more, the first resin layer has excellent mechanical strength. When Mw is 500,000 or less, the first resin layer has excellent moldability.

The melt flow rate (MFR) of the methacrylic resin (A) is not particularly limited, and is preferably 0.1 to 10 g / 10 minutes, more preferably 0.5 to 8 g / 10 minutes, and particularly preferably 1 to 5 g / 10. Minutes. When the MFR is 0.1 to 10 g / 10 minutes, the first resin layer has excellent moldability. In the present specification, "MFR of methacrylic resin (A)" is a value measured under the condition of 230 ° C. and 3.8 kg load according to JIS-K7210.

The glass transition temperature (Tg) of the methacrylic resin (A) is not particularly limited, and is preferably 100 ° C. or higher, more preferably 105 ° C. or higher, and particularly preferably 110 ° C. or higher. When the Tg is 100 ° C. or higher, the first resin layer has excellent heat resistance.

The methacrylic resin (A) can be produced by polymerizing one or more monomers containing MMA in the presence of a polymerization initiator. If necessary, an arbitrary component such as a chain transfer agent can be used for the polymerization. The polymerization method is not particularly limited, and when a radical polymerization method such as a radical polymerization method and an anion polymerization method is used, a suspension polymerization method, a massive polymerization method, a solution polymerization method, or an emulsion polymerization method can be selected. Is. Among them, the suspension polymerization method and the massive polymerization method are preferable from the viewpoint of productivity and heat-decomposability. Bulk polymerization is preferably carried out by a continuous flow method.
As a method of anionic polymerization of the methacrylic resin (A), an organic alkali metal compound is used as a polymerization initiator, and anionic polymerization is performed in the presence of a mineral salt such as an alkali metal or an alkaline earth metal salt (special fairness). 7-25859 (see Japanese Patent Application Laid-Open No. 7-25859), a method of anionic polymerization using an organoalkali metal compound as a polymerization initiator in the presence of an organoaluminum compound (see JP-A-11-335432), and organic rare earths as a polymerization initiator. Examples thereof include a method of anionic polymerization using a metal complex (see JP-A-6-93060).

The various characteristic values of the methacrylic resin (A) described in the present specification are determined by adjusting the polymerization conditions such as the polymerization temperature, the polymerization time, the type and amount of the polymerization initiator, and the type and amount of the chain transfer agent. , Can be adjusted within a preferred range.

<Multilayer rubber particles (C)>
The first resin layer preferably further contains the multilayer structure rubber particles (C) in addition to the methacrylic resin (A). By adding the multilayer structure rubber particles (C) to the first resin layer, the impact resistance of the methacrylic resin laminate of the present invention can be improved. The first resin layer preferably contains 95 to 60% by mass of the methacrylic resin (A) and 5 to 40% by mass of the multilayer structure rubber particles (C). When the content of the multilayer structure rubber particles (C) is in the range of 5 to 40% by mass, the first resin layer has excellent transparency and impact resistance. The first resin layer more preferably contains 93 to 65% by mass of the methacrylic resin (A) and 7 to 35% by mass of the multilayer structure rubber particles (C). It is particularly preferable that the first resin layer contains 90 to 70% by mass of the methacrylic resin (A) and 10 to 30% by mass of the multilayer structure rubber particles (C).

Examples of the multilayer structure rubber particles (C) include acrylic crosslinked rubber particles and diene crosslinked rubber particles. Specifically, copolymer rubber particles containing an acrylic acid ester monomer unit, a crosslinkable monomer unit, and, if necessary, another vinyl-based monomer unit; a conjugated diene-based monomer unit, cross-linking. Copolymer rubber particles containing a sex monomer unit and, if necessary, other vinyl monomer units; acrylic acid ester monomer unit, conjugated diene monomer unit, crosslinkable monomer unit, And, if necessary, copolymer rubber particles containing other vinyl-based monomer units and the like can be mentioned.

As the multilayer structure rubber particles (C), acrylic multilayer structure rubber particles are preferable. From the viewpoint of improving light resistance, acrylic multilayer rubber particles containing no conjugated diene-based monomer unit are more preferable. The acrylic multilayer structure rubber particles have a core portion and a shell portion. The core portion includes a central layer and an intermediate layer, and the shell portion is composed of an outermost layer covering the core portion. In the acrylic multilayer structure rubber particles, the intermediate layer contains a crosslinked rubber polymer (i), and the central layer contains a polymer (iii) other than the crosslinked rubber polymer.

The crosslinked rubber polymer (i) contains at least an acrylic ester monomer unit and a crosslinkable monomer unit.
As the acrylic acid ester monomer used as a raw material of the crosslinked rubber polymer (i), an acrylic acid ester monomer having an alkyl group having 1 to 8 carbon atoms and an aromatic group having 6 to 24 carbon atoms are used. Acrylic ester monomers and the like are preferable. Specifically, methyl acrylate, ethyl acrylate, propyl acrylate, butyl acrylate, 2-ethylhexyl acrylate, phenyl acrylate, benzyl acrylate, paracumylphenolethylene oxide modified acrylate, and o-phenylphenolethylene oxide. Modified acrylate and the like can be mentioned. These can be used alone or in combination of two or more.
The content of the acrylic ester monomer unit in the crosslinked rubber polymer (i) is preferably 60% by mass or more, more preferably 70 to 99% by mass, and particularly preferably 80 to 98% by mass.

Examples of the crosslinkable monomer used as a raw material for the crosslinked rubber polymer (i) include allyl acrylate, allyl methacrylate, 1-acryloxy-3-butene, 1-methacryloxy-3-butene, and 1,2-diacryloxy-. Ethan, 1,2-dimethacryloxy-ethane, 1,2-diacryloxy-propane, 1,3-diacryloxy-propane, 1,4-diacryloxy-butane, 1,3-dimethacryloxy-propane, 1,2-dimethacryloxy-propane, Examples thereof include 1,4-dimethacryloxy-butane, triethylene glycol dimethacrylate, hexanediol dimethacrylate, triethylene glycol diacrylate, hexanediol diacrylate, divinylbenzene, 1,4-pentadiene, and triallyl isocyanate. These can be used alone or in combination of two or more.
The content of the crosslinkable monomer unit in the crosslinked rubber polymer (i) is preferably 0.05 to 10% by mass, more preferably 0.5 to 7% by mass, and particularly preferably 1 to 5% by mass. is there.

The crosslinked rubber polymer (i) may contain other vinyl-based monomer units other than the above. The other vinyl-based monomer is not particularly limited as long as it can be copolymerized with the above acrylic ester monomer and crosslinkable monomer. Other vinyl-based monomers include methacrylic acid ester monomers such as methyl methacrylate, ethyl methacrylate, butyl methacrylate, phenyl methacrylate, benzyl methacrylate, and cyclohexyl methacrylate; styrene, p-methylstyrene, and the like. Aromatic vinyl monomers such as o-methylstyrene; and maleimide-based monomers such as N-propylmaleimide, N-cyclohexylmaleimide, and NO-chlorophenylmaleimide can be mentioned. These can be used alone or in combination of two or more.

The polymer (iii) is not particularly limited as long as it is a polymer other than the crosslinked rubber polymer (i), and a polymer containing a methacrylic acid ester monomer unit is preferable. The polymer (iii) may contain a crosslinkable monomer unit and / or other vinyl-based monomer unit in addition to the methacrylic acid ester monomer unit.
Examples of the methacrylic acid ester monomer used as a raw material of the polymer (iii) include a methacrylic acid ester monomer having an alkyl group having 1 to 8 carbon atoms and a methacrylic acid having an aromatic group having 6 to 24 carbon atoms. Acid ester monomers and the like are preferred. Specific examples thereof include methyl methacrylate (MMA), ethyl methacrylate, butyl methacrylate, phenyl methacrylate, benzyl methacrylate and the like. These can be used alone or in combination of two or more. Of these, methyl methacrylate (MMA) is preferred.
The content of the methacrylic acid ester monomer unit in the polymer (iii) is preferably 40 to 100% by mass, more preferably 50 to 99% by mass, and particularly preferably 60 to 98% by mass.

Examples of the crosslinkable monomer used as a raw material for the polymer (iii) as needed are the same as those for the crosslinkable monomer used as a raw material for the crosslinked rubber polymer (i). The content of the crosslinkable monomer unit in the polymer (iii) is preferably 0 to 5% by mass, more preferably 0.01 to 3% by mass, and particularly preferably 0.02 to 2% by mass.

The other vinyl-based monomer used as a raw material for the polymer (iii), if necessary, is not particularly limited as long as it can be copolymerized with the above-mentioned methacrylic acid ester monomer and crosslinkable monomer. For example, methyl acrylate, ethyl acrylate, propyl acrylate, butyl acrylate, hexyl acrylate, cyclohexyl acrylate, phenyl acrylate, benzyl acrylate, 2-ethylhexyl acrylate, paracumylphenol ethylene oxide modified acrylate, and o. -Acrylic acid ester monomer such as phenylphenol ethylene oxide modified acrylate; Vinyl acetate; Aromatic vinyl simple such as styrene, p-methylstyrene, m-methylstyrene, o-methylstyrene, α-methylstyrene, and vinylnaphthalene. Quantities; nitriles such as acrylonitrile and methacrylonitrile; α, β-unsaturated carboxylic acids such as acrylic acid, methacrylic acid, and crotonic acid; and maleimide-based singles such as N-ethylmaleimide and N-cyclohexylmaleimide. Quantitative substances and the like can be mentioned. These can be used alone or in combination of two or more.

The outermost layer contains a thermoplastic polymer (ii). The thermoplastic polymer (ii) contains at least a methacrylic acid ester monomer unit and, if necessary, another vinyl-based monomer unit.
As the methacrylic acid ester monomer used as a raw material of the thermoplastic polymer (ii), a methacrylic acid ester monomer having an alkyl group having 1 to 8 carbon atoms and an aromatic group having 6 to 24 carbon atoms are used. Preferably having a methacrylic acid ester or the like. Specific examples thereof include methyl methacrylate (MMA), butyl methacrylate, phenyl methacrylate, benzyl methacrylate and the like. These can be used alone or in combination of two or more. Of these, methyl methacrylate (MMA) is preferred.
The content of the methacrylic acid ester monomer unit in the thermoplastic polymer (ii) is preferably 40% by mass or more, more preferably 50% by mass or more, and particularly preferably 60% by mass or more.

Examples of other vinyl-based monomers used as a raw material for the thermoplastic polymer (ii) as needed include other vinyl-based monomers used as a raw material for the above-mentioned polymer (iii) as needed. It is the same as the example of. The content of the other vinyl-based monomer unit in the thermoplastic polymer (ii) is preferably 60% by mass or less, more preferably 50% by mass or less, and particularly preferably 40% by mass or less.

From the viewpoint of the transparency of the acrylic multilayer rubber particles, the difference in refractive index between adjacent layers is preferably less than 0.005, more preferably less than 0.004, and particularly preferably less than 0.003. , It is preferable to select the polymer contained in each layer.

The proportion of the outermost layer in the acrylic multilayer structure rubber particles is preferably 10 to 60% by mass, more preferably 15 to 50% by mass, and particularly preferably 20 to 40% by mass. In the core portion, the proportion of the layer containing the crosslinked rubber polymer (i) is preferably 20 to 100% by mass, more preferably 30 to 70% by mass.

The volume-based average particle diameter of the multilayer structure rubber particles (C) is not particularly limited, and is preferably 0.02 to 1 μm, more preferably 0.05 to 0.05 from the viewpoint of transparency and impact resistance of the first resin layer. It is 0.5 μm, particularly preferably 0.1 to 0.3 μm. In the present specification, unless otherwise specified, the "volume-based average particle size" is calculated based on the particle size distribution data measured by the light scattered light method.

The method for producing the multilayer structure rubber particles (C) is not particularly limited. The emulsification polymerization method, particularly the seed emulsification polymerization method, is preferable from the viewpoint of controlling the particle size and easiness of producing the multilayer structure.
In the emulsion polymerization method, a polymer particle is formed by adding a polymerization initiator to a raw material solution obtained by mixing a medium such as water, one or more monomers poorly soluble in the medium, and an emulsifier, and polymerizing the mixture. It is a method for producing an emulsion containing.
In the seed emulsion polymerization method, seed particles are obtained by emulsifying and polymerizing one or more kinds of monomers, and another one or more kinds of monomers are emulsified and polymerized in the presence of the seed particles to obtain seed particles. This is a method for producing an emulsion containing core-shell polymer particles containing a shell polymer layer that coats it substantially concentrically. In the seed emulsion polymerization method, one or more other monomers can be emulsion-polymerized in the presence of the obtained core-shell polymer particles. This operation can be repeated a plurality of times as needed. By this method, an emulsion containing core-shell multilayer polymer particles having seed particles and a plurality of shell polymer layers covering the seed particles substantially concentrically can be produced.

<Arbitrary component of the first resin layer>
The first resin layer may contain a polymer other than the methacrylic resin (A) and the multilayer structure rubber particles (C) as long as the effects of the present invention are not impaired. Other polymers include polyolefins such as polyethylene, polypropylene, polybutene-1, poly-4-methylpentene-1, and polynorbornene; ethylene-based ionomers; polystyrene, high-impact polystyrene, SMA resin, SMM resin, AS resin, etc. Sterite resins such as ABS resin, AES resin, AAS resin, ACS resin, and MBS resin; methyl methacrylate-styrene copolymer; polyesters such as polyethylene terephthalate and polybutylene terephthalate; nylon 6, nylon 66, and polyamide elastomer Polyene such as: polyphenylene sulfide, polyether ether ketone, polysulfone, polyphenylene oxide, polyimide, polyetherimide, polycarbonate, polyvinyl chloride, polyvinylidene chloride, vinylidene fluoride, polyvinyl alcohol, ethylene-vinyl alcohol copolymer, and polyacetal. Other thermoplastic resins such as: phenolic resins, melamine resins, silicone resins, and thermocurable resins such as epoxy resins; polyurethanes; modified polyphenylene ethers; silicone modified resins; acrylic block copolymers, silicones, etc. Rubbers; 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 first resin layer is not particularly limited, and is preferably 20% by mass or less, more preferably 15% by mass or less, and particularly preferably 10% by mass or less.

The first resin layer may contain various additives, if necessary. Additives include antioxidants, heat deterioration inhibitors, UV absorbers, light stabilizers, lubricants, mold release agents, polymer processing aids, antistatic agents, flame retardants, dyes / pigments, light diffusers, and luster. Examples thereof include erasers, impact-resistant modifiers, fillers, and phosphors. The content of the additive can be appropriately set as long as the effect of the present invention is not impaired. For example, the content of the antioxidant is preferably 0.01 to 1% by mass, the content of the ultraviolet absorber is preferably 0.01 to 3% by mass, and the content of the light stabilizer is preferably 0.01 to 3% by mass. The mass%, the content of the lubricant is preferably 0.01 to 3% by mass, and the content of the dye / pigment is preferably 0.01 to 3% by mass.

(Second resin layer)
<Thermoplastic elastomer (B)>
The second resin layer is a block copolymer containing a polymer block (b-1) containing an aromatic vinyl monomer unit and a polymer block (b-2) containing a conjugated diene monomer unit, or a block copolymer thereof. Includes a thermoplastic elastomer (B) that is a hydrogenated block copolymer.
The shatterproof performance of the second resin layer tends to improve as the content of the thermoplastic elastomer (B) increases. However, as the content of the thermoplastic elastomer (B) increases, the elastic modulus of the second resin layer tends to decrease, and the bending rigidity tends to decrease. In the present invention, this defect is solved by laminating the first resin layer containing the methacrylic resin (A) on both sides of the second resin layer containing the thermoplastic elastomer (B). According to the present invention, for example, it is possible to provide a methacrylic resin laminate having a flexural modulus of 1500 MPa or more. The flexural modulus can be measured by the method described in the section [Example] below.

The bond form between the polymer block (b-1) and the polymer block (b-2) is not particularly limited, and may be a linear bond, a branched bond, a radial bond, or a combination thereof, and is linear. The state bond is preferable.
Here, the polymer block (b-1) is referred to as “a”, and the polymer block (b-2) is referred to as “b”. As the linear bonding form, a diblock copolymer represented by ab, a triblock copolymer represented by ab-a or b-а-b, ab-ab Tetrablock copolymer represented by, pentablock copolymer represented by a-b-a-ba-a or b-a-b-ab, (а-b) _n- X type copolymer. (Here, the reference numeral X represents a coupling residue, n represents an integer of 2 or more), and combinations thereof can be mentioned. Of these, diblock copolymers or triblock copolymers are preferable. As the triblock copolymer, the triblock copolymer represented by a-ba-a is particularly preferable.

The total content of the aromatic vinyl monomer unit and the conjugated diene monomer unit in the block copolymer is preferably 80% by mass or more, more preferably 95% by mass or more, and particularly preferably 98% by mass or more. ..

The content of the aromatic vinyl monomer unit in the block copolymer is preferably 5 to 40% by mass, more preferably 10 to 30% by mass, and particularly preferably 12 to 20% by mass. When the content of the aromatic vinyl monomer unit is 5% by mass or more, the methacrylic resin laminate of the present invention has excellent moldability. When the content of the aromatic vinyl monomer unit is 40% by mass or less, the interlayer adhesiveness between the first resin layer and the second resin layer becomes excellent. The content of the aromatic vinyl monomer unit can be determined from the charged composition of the raw material monomer when synthesizing the block copolymer ^{or the measurement result of 1 H-NMR of the block copolymer.}
The polymer block (b-1) may contain a small amount of other monomer units in addition to the aromatic vinyl monomer unit. The proportion of the aromatic vinyl monomer unit in the polymer block (b-1) is preferably 80% by mass or more, more preferably 95% by mass or more, and particularly preferably 98% by mass or more.

Examples of the aromatic vinyl monomer include styrene (St); α-methylstyrene, 2-methylstyrene, 3-methylstyrene, 4-methylstyrene, 4-propylstyrene, 4-cyclohexylstyrene, 4-dodecylstyrene and the like. Alkylstyrene; arylstyrene such as 2-ethyl-4-benzylstyrene, 4- (phenylbutyl) styrene, 1-vinylnaphthalene, and 2-vinylnaphthalene; styrene halide; alkoxystyrene; vinyl benzoic acid ester and the like. Be done. Among them, styrene (St) and α-methylstyrene are preferable, and α-methylstyrene is more preferable. These can be used alone or in combination of two or more.

The content of the conjugated diene polymer block (b-2) in the block copolymer is preferably 60 to 78% by mass, more preferably 62 to 76% by mass, and particularly preferably 64 to 74% by mass. When the content of the conjugated diene polymer block (b-2) is at least the above lower limit, the characteristics as an elastomer are satisfactorily exhibited. When the content of the conjugated diene polymer block (b-2) is not more than the above upper limit, the moldability of the methacrylic resin laminate of the present invention becomes excellent. The content of the conjugated diene monomer unit can be determined from the charged composition of the raw material monomer when synthesizing the block copolymer and ^{the measurement results of 1 H-NMR of the block copolymer.}
The polymer block (b-2) may contain a small amount of other monomer units in addition to the conjugated diene monomer unit. The proportion of the conjugated diene monomer unit in the polymer block (b-2) is preferably 80% by mass or more, more preferably 95% by mass or more, and particularly preferably 98% by mass or more.
As the conjugated diene, a conjugated diene having 2 to 12 carbon atoms is preferable, and a conjugated diene having 4 to 8 carbon atoms is more preferable, from the viewpoint of availability and handleability. Specifically, 1,3-butadiene, isoprene, and combinations thereof are particularly preferable.

The thermoplastic elastomer (B) may be a hydrogenated product in which at least a part of the conjugated diene monomer units of the block copolymer is hydrogenated (also referred to as hydrogenation). Generally, a styrene-based thermoplastic elastomer hydrogenated with at least a part of conjugated diene monomer units is referred to as "hydrogenated styrene-based thermoplastic elastomer". The hydrogenation rate is preferably 80% or more, more preferably 90% or more. The "hydrogenation rate" is obtained by measuring the iodine value of the block copolymer before and after the hydrogenation reaction.

Examples of the polymerization method of the block copolymer (unhydrogenated thermoplastic elastomer) include an anion polymerization method, a cationic polymerization method, and a radical polymerization method.
In the case of anionic polymerization, for example, (i) a method of using an alkyllithium compound as a polymerization initiator to sequentially polymerize an aromatic vinyl monomer, a conjugated diene monomer, and an aromatic vinyl monomer; (ii) polymerization. A method in which an alkyllithium compound is used as an initiator, an aromatic vinyl monomer and a conjugated diene monomer are sequentially polymerized, and a coupling agent is further added for coupling; (iii) a dilithium compound is used as a polymerization initiator. Examples thereof include a method of sequentially polymerizing a conjugated diene monomer and an aromatic vinyl monomer.

By adding an organic Lewis base during anionic polymerization, the 1,2-bonding amount and 3,4-bonding amount of the thermoplastic elastomer can be increased. Furthermore, the amount of 1,2-bonding and the amount of 3,4-bonding of the thermoplastic elastomer can be adjusted by the amount of the organic Lewis base added.
Examples of the organic Lewis base include esters such as ethyl acetate; amines such as triethylamine, N, N, N', N'-tetramethylethylenediamine (TMEDA), and N-methylmorpholin; nitrogen-containing heterocyclic aromatics such as pyridine. Compounds; Amides such as dimethylacetamide; Ethers such as dimethyl ether, diethyl ether, tetrahydrofuran (THF), and dioxane; Glycol ethers such as ethylene glycol dimethyl ether and diethylene glycol dimethyl ether; Sulfoxides such as dimethyl sulfoxide; Ketones such as acetone and methyl ethyl ketone. Be done.

A reaction solution containing a block copolymer (unhydrogenated thermoplastic elastomer) polymerized by a known method, or a block copolymer (unhydrogenated thermoplastic elastomer) isolated from this reaction solution is used as a hydrogenation catalyst. On the other hand, a hydrogenated thermoplastic elastomer can be obtained by preparing a solution dissolved in an inert solvent and reacting with hydrogen in the presence of a hydrogenation catalyst.
The hydrogenation catalyst includes Raney nickel; a heterogeneous catalyst in which a metal such as Pt, Pd, Ru, Rh, and Ni is supported on a carrier such as carbon, alumina, and diatomaceous earth; a transition metal compound and an alkylaluminum compound or alkyllithium. A Cheegler-based catalyst composed of a combination with a compound or the like; a metallocene-based catalyst or the like can be mentioned. The hydrogenation reaction can usually be carried out under the conditions of a hydrogen pressure of 0.1 to 20 MPa, a reaction temperature of 20 to 250 ° C., and a reaction time of 0.1 to 100 hours.

The thermoplastic elastomer (B) may be one in which a part of the molecular chain and / or the molecular end is modified with a polar functional group. The polar functional group is preferably introduced at the terminal of at least one molecule. Examples of the polar functional group include an acid anhydride group such as a maleic anhydride group; a carboxy group; a dicarboxy group such as a maleic acid group; an amino group; an imino group; an alkoxysilyl group; a silanol group; a silyl ether group; a hydroxyl group; Examples include epoxy.

The weight average molecular weight (Mw) of the thermoplastic elastomer (B) is preferably 30,000 to 400,000, more preferably 50,000 to 300,000 from the viewpoint of mechanical properties and moldability. The molecular weight distribution (Mw / Mn), which is the ratio of the weight average molecular weight (Mw) to the number average molecular weight (Mn) of the thermoplastic elastomer (B), is preferably 1.0 to 2.0, more preferably 1.0 to 1.0. It is 1.5. In the present specification, "Mw" is a polystyrene-equivalent weight average molecular weight determined by gel permeation chromatography (GPC) measurement. "Mn" is a polystyrene-equivalent number average molecular weight determined by GPC measurement.

In the present invention, as the thermoplastic elastomer (B), dynamic viscoelasticity measurement is carried out under the condition of a frequency of 1.0 Hz in accordance with JIS-K7244-4, and the data of the change in loss tangent (tan δ) with respect to temperature (tan δ). When the tan δ curve) is obtained, the peak of at least one loss tangent (tan δ) is in the temperature range of -60 to -30 ° C, preferably in the temperature range of -55 to -35 ° C, more preferably -50 to -40. Use a thermoplastic elastomer in the temperature range of ° C. The methacrylic resin laminate of the present invention using the thermoplastic elastomer (B) having such physical characteristics is excellent in anti-scattering property in a wide temperature range including a low temperature range.

By adjusting the raw material composition and / or polymerization conditions of the thermoplastic elastomer (B), it is possible to obtain a thermoplastic elastomer having at least one loss tangent (tan δ) peak in the temperature range of −60 to −30 ° C. .. In the thermoplastic elastomer (B) having a peak loss tangent (tan δ) in the temperature range of −60 ° C. to −30 ° C., the conjugated diene monomer unit constituting the polymer block (b-2) is an isoprene unit. In this case, the degree of vinylization is preferably 0 to 40 mol%, and when the conjugated diene monomer unit constituting the polymer block (b-2) is a butadiene unit, the degree of vinylization is 40 to 70 mol%. Is preferable.
In the conjugated diene monomer unit, the "degree of vinylization" is 1, with respect to the sum of the amount of 1,2-bonding unit, the amount of 3,4-bonding unit, and the amount of 1,4-bonding unit. It can be obtained by the ratio of the sum of the amount of 2-bonding unit and the amount of 3,4-binding unit.

<Methacrylic resin (D)>
The second resin layer preferably contains one or more methacrylic resins (D) in accordance with the thermoplastic elastomer (B) composed of a block copolymer or a hydrogenated product thereof. When the second resin layer contains the methacrylic resin (D), the transparency and rigidity of the second resin layer are improved, and the compatibility with the first layer containing the methacrylic resin (A) is further improved. Therefore, the interlayer adhesiveness between the first resin layer and the second resin layer is improved. As the methacrylic resin (D), any known methacrylic resin can be used, and the preferable structure and physical properties are the same as those of the methacrylic resin (A) contained in the first resin layer. Please refer to the section of (1st resin layer). The methacrylic resin (A) in the first resin layer and the methacrylic resin (D) in the second resin layer may be the same or non-identical.

From the viewpoint of the transparency of the second resin layer, the methacrylic resin (D) contains 80% by mass or more of the methyl methacrylate (MMA) monomer unit and 5% by mass of the methyl acrylate (MA) monomer unit. It is preferable to include the above.
The weight average molecular weight (Mw) of the methacrylic resin (D) is not particularly limited, and is preferably 80,000 or less, more preferably 50,000 or less, particularly preferably 45,000 or less, and particularly preferably 40,000. .. When Mw is 80,000 or less, the second resin layer has excellent transparency.

The contents of the thermoplastic elastomer (B) and the methacrylic resin (D) in the second resin layer are not particularly limited. Since the second resin layer is excellent in transparency, the second resin layer preferably contains 95 to 60% by mass of the thermoplastic elastomer (B) and 5 to 40% by mass of the methacrylic resin (D). It is more preferable to contain 90 to 65% by mass of the thermoplastic elastomer (B) and 10 to 35% by mass of the methacrylic resin (D), and 85 to 70% by mass of the thermoplastic elastomer (B) and the methacrylic resin (D) 15. It is particularly preferable to contain ~ 30% by mass.

When the second resin layer contains the thermoplastic elastomer (B) and the methacrylic resin (D), examples of the method for mixing these resins include a melt mixing method and a solution mixing method. In the melt-mixing method, a single-screw or double-screw kneading extruder, an open roll, a Banbury mixer, and a melt-kneader such as a kneader are used, and if necessary, the inert gas such as nitrogen gas, argon gas, and helium gas is used. Melt kneading can be performed in a gas atmosphere. In the solution mixing method, the thermoplastic elastomer (B) and the methacrylic resin (D) can be dissolved in an organic solvent which is a good solvent for both and mixed. Among these mixing methods, the melt mixing method is preferable, and the method using a single-screw or twin-screw kneading extruder is particularly preferable. The temperature at the time of mixing and kneading can be appropriately adjusted according to the melting temperature of the thermoplastic elastomer (B) and the methacrylic resin (D) to be used, and is preferably 110 to 300 ° C.

<Arbitrary component of the second resin layer>
The second resin layer may contain a polymer other than the thermoplastic elastomer (B) and the methacrylic resin (D) and / or various additives as long as the effects of the present invention are not impaired. The types and preferable contents of other polymers and various additives that can be used are the same as those of the first resin layer, and refer to the above section (first resin layer).

When the second resin layer containing the thermoplastic elastomer (B) contains an optional component, the optional component may be mixed with the thermoplastic elastomer (B) or added at the time of polymerization of the thermoplastic elastomer (B). May be good.
When an optional component is contained in the second resin layer containing the thermoplastic elastomer (B) and the methacrylic resin (D), the optional component is used during the polymerization of the thermoplastic elastomer (B) and / or the methacrylic resin (D). It may be added, or may be added at the time of mixing the thermoplastic elastomer (B) and the methacrylic resin (D) or after mixing.

(Laminated structure)
The methacrylic resin laminate of the present invention includes a laminated structure in which a first resin layer containing a methacrylic resin (A) is laminated on both sides of a second resin layer containing a thermoplastic elastomer (B). It is a laminated body having three or more layers which may have a resin layer other than the one resin layer and the second resin layer.
The constituent resins of the other resin layers are not particularly limited, and one or more thermoplastic resins excluding the methacrylic resin (A) and the thermoplastic elastomer (B), one or more thermosetting resins, One type or two or more types of energy ray curable resins, and combinations thereof can be mentioned.
The functions of the other resin layers are not particularly limited, and the other resin layers include a support layer, a scratch resistant layer, an antistatic layer, an antifouling layer, and a friction reducing layer that support the first resin layer and the second resin layer. It may function as various functional layers such as an antiglare layer, an antireflection layer, an adhesive layer, a heat ray absorbing layer, a sound insulating 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 the methacrylic resin laminate of the present invention, the thickness of the first resin layer is not particularly limited, and is preferably 0.1 to 10.10 from the viewpoint of scratch resistance, weather resistance, rigidity, impact resistance, and the like. It is 0 mm, more preferably 0.5 to 8.0 mm, and particularly preferably 1.0 to 5.0 mm.
In the methacrylic resin laminate of the present invention, the thickness of the second resin layer is not particularly limited, and is preferably 0.01 to 5.0 mm, more preferably 0.01 to 5.0 mm, from the viewpoint of rigidity, weather resistance, shatterproofness, and the like. Is 0.05 to 4.0 mm, particularly preferably 0.1 to 2.5 mm.
The overall thickness of the methacrylic resin laminate of the present invention is not particularly limited, and is preferably 0.1 to 15.0 mm, more preferably 0.5 to 10.0 mm, from the viewpoint of being able to be produced with good productivity without poor appearance. Particularly preferably, it is 1.0 to 8.0 mm.

In the methacrylic resin laminate of the present invention, the ratio of the total thickness of the two first resin layers to the total thickness is preferably 50% or more, more preferably 60% or more, and particularly preferably 70% or more. Most preferably, it is 80% or more. When the ratio of the total thickness of the two first resin layers to the total thickness is 50% or more, the methacrylic resin laminate of the present invention is excellent in transparency and rigidity.

The method for producing the methacrylic resin laminate of the present invention having a three-layer structure composed of two first resin layers and a second resin layer sandwiched between them is not particularly limited, and a known multi-layer molding is used. It is preferable to manufacture. Examples of the multi-layer molding include a multi-layer extrusion molding; a multi-layer blow molding; a multi-layer press molding; a multi-color injection molding; a pasting synthetic molding method such as an insert injection molding. Multilayer extrusion is preferred from the standpoint of productivity. In addition, in this specification, "multi-layer molding" means laminating molding of two or more layers.

The methacrylic resin laminate of the present invention having a laminated structure of four or more layers including two first resin layers, a second resin layer sandwiched between them, and one or more other resin layers. The production method is not particularly limited, and a method of multi-layer molding one or more other resin layers together with the two first resin layers and the second resin layer by the above method, and two first resin layers by the above method. After producing a three-layer structure laminate composed of a second resin layer sandwiched between the resin and the resin layer, another fluid resin is applied to the surface of one of the first resin layers and dried or solidified. After producing a three-layer structure laminate composed of two first resin layers and a second resin layer sandwiched between them by the method of curing and the above method, one of the first resin layers Examples thereof include a method of adhering another resin layer to the surface via an adhesive layer or the like, a combination thereof, and the like.

Multi-layer extrusion can be carried out by a known method, with two first resin layers, a second resin layer sandwiched between them, and one or more other resin layers, if necessary. It can be laminated by melt coextrusion. A T-die that extrudes the raw material resin (composition) of each layer in a molten state into a sheet in a laminated state, and a plurality of sheets arranged adjacent to each other that pressurize the molten sheet-like laminated body extruded from the T-die while cooling. It is preferable to carry out multi-layer extrusion molding using an apparatus equipped with a roll unit made of the above rolls.

The laminating method includes a feed block method in which the raw material resin (composition) of each layer in the molten state is laminated before the inflow of the T die, and a multi-manifold method in which the raw material resin (composition) of each layer in the molten state is laminated inside the T die. The method can be mentioned. Above all, the multi-manifold method is preferable from the viewpoint of improving the interfacial smoothness between each layer of the laminated body.
Examples of the roll constituting the roll unit include a polishing roll having a mirror-finished roll surface; a rubber roll in which rubber is wound around the surface of a metal, stainless steel, and carbon steel core; and a fine embossed pattern (unevenness pattern) on the roll surface. ), And the like.

The raw material resin (composition) for each layer of the laminate is preferably filtered by a filter before and / or during multilayer molding. By multi-layer molding using the filter-filtered raw material resin (composition), a laminate having few defects caused by foreign substances and gel can be obtained. The material of the filter used is not particularly limited, and is appropriately selected according to the operating temperature, viscosity, filtration accuracy, etc., and is a non-woven fabric made of polypropylene, polyester, rayon, cotton, glass fiber, etc .; phenolic resin impregnated cellulose film. ; Metal fiber non-woven fabric sintered film; metal powder sintered film; wire mesh; and combinations thereof. Above all, from the viewpoint of heat resistance and durability, it is preferable to use a plurality of laminated metal fiber non-woven fabric sintered films. The opening diameter of the filter is not particularly limited, and is preferably 30 μm or less, more preferably 10 μm or less, and particularly preferably 5 μm or less.

As described above, according to the present invention, a methacrylic resin laminate having the original characteristics such as transparency and rigidity of a methacrylic resin and having anti-scattering properties in a wide temperature range including a low temperature range. Can be provided.

[Use]
The methacrylic resin laminate of the present invention is, for example, a signboard component or marking film such as an advertising tower, a stand signboard, a sleeve signboard, a column signboard, and a roof signboard; a display component such as a showcase, a partition plate, and a store display; a fluorescent lamp. Lighting parts such as covers, mood lighting covers, lamp shades, light ceilings, light walls, and chandeliers; Interior parts such as furniture, pendants, and mirrors; Exterior decorations such as doors, dome, and FRP; Safety windowpanes, partitions , Staircase wainscots, balcony wainscots, and building parts such as roofs of leisure buildings; aircraft windshields, pilot visors, motorcycles, motorboat windshields, bus shading plates, automotive interior / exterior components (side visors, rear visors, head wings) , Headlight covers, bumpers, sun roofs, glazing, etc.), etc.); Sound and image nameplates, stereo covers, TV protective masks; Medical equipment parts such as incubators and roentgen parts; Machine covers, instrument covers, experiments Equipment-related parts such as devices, rulers, dials, and observation windows; optical parts such as liquid crystal protective plates, light guide plates, light guide films, frennel lenses, lenticular lenses, front plates of various displays, and diffuser plates; road signs , Information boards, curved mirrors, and traffic-related parts such as soundproof walls; bathroom parts such as greenhouses, large water tanks, box water tanks, bathtubs, clock panels, sanitary, desk mats, game parts, toys, face protection masks during welding Examples include surface materials used for personal computers, mobile phones, furniture, vending machines, bathroom members, and the like.

The methacrylic resin laminate of the present invention has characteristics such as transparency, weather resistance, and rigidity, which are the characteristics of the methacrylic resin, and has anti-scattering properties in a wide temperature range including a low temperature range. Glazing for moving objects such as windows and canopies; Machine covers for protecting machine tools and their viewing windows; Can be suitably used for sound insulation plates and protective plates used on highways and high-speed railways.

Examples and comparative examples according to the present invention will be described.
[Evaluation items and evaluation methods]
(Weight average molecular weight (Mw), molecular weight distribution (Mw / Mn))
The weight average molecular weight (Mw) of the resin and the molecular weight distribution (Mw / Mn), which is the ratio of the weight average molecular weight (Mw) to the number average molecular weight (Mn), were determined by the GPC method (gel permeation chromatography method). .. Tetrahydrofuran (THF) was used as the eluent. As the column, a column in which two TSKgel SuperMultipore HZM-M manufactured by Tosoh Corporation and one SuperHZ4000 were connected in series was used. As the GPC apparatus, HLC-8320 (product number) manufactured by Tosoh Corporation equipped with a differential refractive index detector (RI detector) was used. A sample solution was prepared by dissolving 4 mg of the resin to be measured in 5 ml of THF. The temperature of the column oven was set to 40 ° C., the eluent flow rate was 0.35 ml / min, 20 μl of the sample solution was injected into the apparatus, and the chromatogram was measured. 10 points of standard polystyrene having a molecular weight in the range of 400 to 500000 were measured by GPC, and a calibration curve showing the relationship between the retention time and the molecular weight was prepared. Based on this calibration curve, Mw and Mw / Mn of the resin to be measured were determined.

(Peak of loss tangent (tan δ))
The thermoplastic elastomer (B) or the thermoplastic elastomer composition (RB) was hot-pressed at 200 ° C. to prepare a film having a thickness of 300 μm. A strip-shaped test piece (a) having a length of 20 mm, a width of 5 mm, and a thickness of 300 μm was cut out from this film. This test piece (a) was subjected to dynamic viscoelasticity measurement in accordance with JIS-K7244-4. Using a viscoelasticity measuring device (“Rheogel-E4000” manufactured by UBM Co., Ltd.), a heating rate of 3 ° C./min, a measurement temperature range of -100 to 180 ° C., a frequency of 1.0 Hz, a strain amplitude of 0.3%, Dynamic viscoelasticity measurement was performed under the condition of tension mode, and data (tanδ curve) of change in loss tangent (tanδ) with respect to temperature was obtained. In this tan δ curve, it was confirmed whether or not there was at least one tan δ peak in the temperature range of -60 to -30 ° C.

(transparency)
The obtained laminated sheet or single-layer sheet was cut to obtain a test piece (b) having a size of 50 mm × 50 mm × thickness 4.0 mm. The total light transmittance and haze of this test piece (b) were measured using a spectrocolorimeter (“SE5000” manufactured by Nippon Denshoku Kogyo Co., Ltd.) in accordance with JIS-K7361. The evaluation criteria are as follows.
<Total light transmittance>
Good (○): Total light transmittance is 90% or more.
Possible (△): Total light transmittance is 85% or more and less than 90%.
Defective (x): Total light transmittance is less than 85%.
<Haze value>
Good (○): Haze value is less than 1%.
Possible (△): Haze value is 1% or more and less than 5%.
Defective (x): Haze value is 5% or more.
<Transparency>
Good (○): Judgment of total light transmittance and haze value is good (○).
Defective (x): The judgment of the total light transmittance and the haze value is both defective (x).
Possible (Δ): A combination other than the above for determining the total light transmittance and the haze value.

(rigidity)
The obtained laminated sheet or single-layer sheet was cut so that the extrusion direction was in the major axis direction to obtain a test piece (c) having a size of 80 mm × 10 mm × thickness 4.0 mm. The flexural modulus at 23 ° C. was measured for this test piece (c) using an autograph (“AG-1S” manufactured by Shimadzu Corporation) and in accordance with JIS-K7171. The evaluation criteria are as follows.
Good (○): Flexural modulus is 1500 MPa or more.
Possible (Δ): Bending elastic modulus is 1000 MPa or more and less than 1500 MPa.
Defective (x): Bending elastic modulus is less than 1000 MPa.

(durability)
The obtained laminated sheet or single-layer sheet was cut to obtain a test piece (b) having a size of 50 mm × 50 mm × thickness 4.0 mm. The following boiling test (I) and heat cycle test (II) were sequentially carried out on one and the same test piece (b).
<Boil test (I)>
The test piece (b) was left in an environment with a temperature of 23 ° C. and a relative humidity of 50% for 1 hour, and then was immersed in warm water at about 65 ° C. for 3 minutes by standing vertically. Then, the test piece (b) was quickly immersed in boiling water for 2 hours and then taken out.
<Heat cycle test (II)>
The test piece (b) subjected to the boiling test (I) was placed in a heat cycle tester. In an environment with a relative humidity of 85%, the temperature is raised to 85 ° C. at a rate of 1 ° C./min, held at this temperature for 4 hours, then lowered to a temperature of −40 ° C. at a rate of 1 ° C./min, and at this temperature. The wet and heat profile held for 4 hours was set as one cycle, and after performing a heat cycle test in which this was repeated for 10 cycles, the test piece (b) was taken out.
After each test, visual observation shows the appearance of poor hue (yellowing, etc.), optical distortion, surface roughness of the outermost layer, wrinkles of the intermediate layer, air bubbles in or between layers, whitening, warpage, layer peeling, cracking, etc. Durability was evaluated by evaluating the presence or absence of defects. The evaluation criteria are as follows.
Good (○): No poor appearance was confirmed after any of the tests.
Possible (Δ): Poor appearance was not confirmed after the boiling test (I), but was confirmed after the heat cycle test (II).
Defective (x): Poor appearance was confirmed after the boiling test (I).

(Prevention of scattering at room temperature and low temperature)
The obtained laminated sheet or single-layer sheet was cut to obtain a test piece (b) having a size of 50 mm × 50 mm × thickness 4.0 mm. A DuPont impact tester (Coating Tester Co., Ltd.) was used as the tester. Using a hemispherical shooting type with a tip of 1/4 inch and a hemispherical cradle with a radius of 1/4 inch, the calculated impact destruction energy value is 0.245J in accordance with JIS-K7211-1. The test was conducted under the conditions (specifically, a weight of 500 g and a weight drop height of 50 cm). The number of fragments separated from the test piece (b) was visually counted. The environmental temperature conditions were two conditions, 23 ° C (normal temperature) and -40 ° C (low temperature). Each test piece was tested under each temperature condition and evaluated according to the following criteria.
Good (○): The number of separated fragments is 0.
Defective (x): The number of separated fragments is 1 or more.

(Impact resistance)
The obtained laminated sheet or single-layer sheet was cut to obtain a test piece (d) having a thickness of 300 mm × 300 mm × thickness of 4.0 mm. The impact resistance of this test piece (d) was evaluated by performing a falling ball impact test in accordance with JIS-R3212. The peripheral edge of the sample, which had been humidity-controlled for 4 hours or more in an environment of 23 ° C. / 50% relative humidity, was fixed to a horizontally supported support frame. A 227 g steel ball having a diameter of 38 mm and a smooth surface was dropped from a height of 2.5 m from the surface of the test piece to the center of the test piece without applying any force in a stationary state. At this time, the steel balls bounced on the test piece were collected so that the impact on one test piece was limited to one time. Twelve test pieces were prepared for each of the laminated sheet or single-layer sheet obtained in each example, a falling ball impact test was performed on each test piece, and the appearance of the test piece after the test was visually observed to check the impact resistance. evaluated. The evaluation criteria are as follows.
Good (○): No cracks or cracks were confirmed in all the test pieces.
Possible (Δ): Cracks and / or cracks were confirmed in at least one test piece, but so-called “missing” in which the steel ball penetrated the test piece was not confirmed in all the test pieces.
Defective (x): Missing was confirmed with at least one test piece.

[Resin raw material]
In the following production examples, examples, and comparative examples, the following resins were used.
(Methacrylic resin (A) or (D))
(A1), (D1): "Parapet" manufactured by Kuraray Co., Ltd., homopolymer (PMMA) of methyl methacrylate (MMA), Mw = 88000, Mw / Mn = 1.9,
(D2): "Parapet" manufactured by Kuraray Co., Ltd., a copolymer of methyl methacrylate (MMA) and methyl acrylate (MA) (MMA / MA (mass ratio) = 86/14), Mw = 37000, Mw / Mn = 1.8.

(Styrene-based thermoplastic elastomer (B))
(B1): A block copolymer (Mst block / EB block (mass ratio) = 33/67) composed of a polyα-methylstyrene (MSt) block and a hydrogenated polyvinylbutazine (EB) block produced in Production Example 1 described later. , Tan δ = -40 ° C, vinylization degree 47 mol%.
(B2): Block copolymer composed of polystyrene (St) block and hydrogenated polyisoprene (EP) block (St block / EP block (mass ratio) = 30/70), tan δ = -40 ° C, degree of vinylization 0 mol%.
(B3): Block copolymer composed of polystyrene (St) block and hydrogenated polyisoprene (EP) block (St block / EP block (mass ratio) = 20/80), tan δ = 5 ° C., vinylization degree 55 Mol%.

(Multilayer structure rubber particles (C))
(C1): Acrylic three-layer structure particles manufactured by Kuraray Co., Ltd. (center layer composition: MMA / MA crosslinked copolymer, intermediate layer composition: BA / St crosslinked copolymer, outermost layer composition: MMA / MA copolymer weight) Combined, volume-based average particle size = 0.23 μm).

[Manufacturing Example 1] (Manufacturing of Styrene-based Thermoplastic Elastomer (B1))
(1) 90.9 g of α-methylstyrene (MSt), 138 g of cyclohexane, 15.2 g of methylcyclohexane, and 5.7 g of tetrahydrofuran (THF) were charged in a pressure-resistant container equipped with a nitrogen-substituted stirrer. 2.1 ml of a 1.3 M cyclohexane solution of sec-butyllithium was added to this mixed solution, and the mixture was polymerized at −10 ° C. for 3 hours (block b-1). Then, 4.4 g of butadiene was added to this reaction solution, and after stirring at −10 ° C. for 30 minutes, 930 g of cyclohexane was added. Next, 158.0 g of butadiene was further added to this reaction solution, and a polymerization reaction was carried out at 50 ° C. for 2 hours.
(2) Subsequently, 2.7 ml of a 0.5 M toluene solution of phenyl benzoate was added to this polymerization reaction solution, and the mixture was stirred at 50 ° C. for 1 hour to obtain α-methylstyrene (MSt) -butadiene-α-methylstyrene. A (MSt) triblock copolymer was obtained. ¹ As a result of 1 H-NMR analysis, the content of α-methylstyrene (MSt) polymer block in this triblock copolymer was 33%, and 1,4- of the entire butadiene polymer block (block b-2). The binding amount was 53 mol%.
(3) A Ziegler-based hydrogenation catalyst formed of nickel octylate and triethylaluminum was added to the polymerization reaction solution obtained in (2) above under a hydrogen atmosphere, and the hydrogen pressure was 0.8 MPa and 80 ° C. was 5 By hydrogenating for a period of time, a styrene-based thermoplastic elastomer (B1) composed of a hydrogenated product of α-methylstyrene (MSt) -butadiene block copolymer was obtained. The hydrogen conversion rate of the butadiene polymer block determined from ^{1 1 H-NMR measurement was 99%.}

[Production Examples 2 and 3] (Production of methacrylic resin compositions (RA1) and (RA2))
The methacrylic resin (A1) and the multi-layered rubber particles (C1) are supplied to the hopper of the twin-screw extruder at the blending ratios shown in Table 1, melt-kneaded at a cylinder temperature of 230 ° C., and extruded to be pelletized methacrylic. The based resin compositions (RA1) and (RA2) were obtained.

[Production Examples 4 to 8] (Production of Styrene-based Thermoplastic Elastomer Compositions (RB1) to (RB5))
The thermoplastic elastomer (B1) or (B2) and the methacrylic resin (D1) or (D2) are supplied to the hopper of the twin-screw extruder at the blending ratios shown in Table 2, and melt-kneaded at a cylinder temperature of 200 ° C. Extrusion molding was performed to obtain pellet-shaped styrene-based thermoplastic elastomer compositions (RB1) to (RB5).

[Example 1]
A methacrylic resin (A1) was prepared as the first resin layer material, and a styrene-based thermoplastic elastomer (B1) was prepared as the second resin layer material.
Pellets of methacrylic resin (A1) 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 230 ° C. and a discharge rate of 25 kg / hr. Pellets of styrene-based thermoplastic elastomer (B1) were continuously charged into a vent-type single-screw extruder having a shaft diameter of 30 mm, and melt-extruded under the conditions of a cylinder temperature of 130 to 210 ° C. and a discharge rate of 3 kg / hr.
The melted methacrylic resin (A1) and the styrene thermoplastic elastomer (B1) are introduced into a junction block, and laminated and extruded (coextruded) from a 400 mm wide multi-manifold die set at 240 ° C. to 100 ° C. The metal mirror surface roll set to 1 and the metal mirror surface roll set to 120 ° C. were pressurized and cooled to form a sheet, which was taken up at a speed of 0.3 m / min.
As described above, the first resin layer (thickness: 1785 μm) made of the methacrylic resin (A1) / the second resin layer (thickness: 450 μm) made of the styrene thermoplastic elastomer (B1) / methacrylic. Laminated sheet (methacrylic resin laminate, total sheet thickness: 4000 μm, two first resin layers with respect to the total thickness) having a three-layer structure of a first resin layer (thickness: 1785 μm) made of resin (A1). The ratio of total thickness: 89%) was obtained. Table 3 shows the composition and evaluation results of each layer of the obtained sheet.

[Examples 2-4, 6-9]
A laminated sheet having a three-layer structure (methacrylic resin laminate) was obtained in the same manner as in Example 1 except that the first resin layer material and the second resin layer material were changed. Table 3 shows the composition and evaluation results of each layer of the obtained sheet.

[Example 5]
A methacrylic resin (A1) was prepared as the first resin layer material, and a styrene-based thermoplastic elastomer composition (RB3) was prepared as the second resin layer material.
In the same manner as in Example 1, pellets of the methacrylic resin (A1) were continuously charged into a vent-type single-screw extruder having a shaft diameter of 50 mm and melt-extruded. Pellets of the styrene-based thermoplastic elastomer composition (RB3) were continuously charged into a vent-type single-screw extruder having a shaft diameter of 30 mm, and melt-extruded under the conditions of a cylinder temperature of 130 to 210 ° C. and a discharge rate of 2 kg / hr.
A sheet was formed and taken over in the same manner as in Example 1 except that the melted methacrylic resin (A1) and the styrene thermoplastic elastomer (RB3) were used.
As described above, the first resin layer (thickness: 1840 μm) made of the methacrylic resin (A1) / the second resin layer (thickness: 320 μm) made of the styrene-based thermoplastic elastomer (BR3) / methacrylic. Laminated sheet (methacrylic resin laminate, total sheet thickness: 4000 μm, two first resin layers with respect to the total thickness) having a three-layer structure of a first resin layer (thickness: 1840 μm) made of resin (A1). The ratio of total thickness: 92%) was obtained. Table 3 shows the composition and evaluation results of each layer of the obtained sheet.

[Example 10]
A methacrylic resin (A1) was prepared as the first resin layer material, and a styrene-based thermoplastic elastomer composition (RB2) was prepared as the second resin layer material.
Pellets of methacrylic resin (A1) 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 230 ° C. and a discharge rate of 14 kg / hr. Pellets of the styrene-based thermoplastic elastomer composition (RB2) were continuously charged into a vent-type single-screw extruder having a shaft diameter of 30 mm, and melt-extruded under the conditions of a cylinder temperature of 130 to 210 ° C. and a discharge rate of 14 kg / hr.
A sheet was formed and taken over in the same manner as in Example 1 except that the above-mentioned molten methacrylic resin (A1) and styrene-based thermoplastic elastomer (RB2) were used.
As described above, the first resin layer (thickness: 1000 μm) made of the methacrylic resin (A1) / the second resin layer (thickness: 2000 μm) made of the styrene-based thermoplastic elastomer (RB2) / methacrylic. Laminated sheet (methacrylic resin laminate, total sheet thickness: 4000 μm, two first resin layers with respect to the total thickness) having a three-layer structure of a first resin layer (thickness: 1000 μm) made of resin (A1). The ratio of total thickness: 50%) was obtained. Table 3 shows the composition and evaluation results of each layer of the obtained sheet.

[Example 11]
A methacrylic resin (A1) was prepared as the first resin layer material, and a styrene-based thermoplastic elastomer composition (RB2) was prepared as the second resin layer material.
Pellets of methacrylic resin (A1) 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 230 ° C. and a discharge rate of 9 kg / hr. Pellets of the styrene-based thermoplastic elastomer composition (RB2) were continuously charged into a vent-type single-screw extruder having a shaft diameter of 30 mm, and melt-extruded under the conditions of a cylinder temperature of 130 to 210 ° C. and a discharge rate of 21 kg / hr.
A sheet was formed and taken over in the same manner as in Example 1 except that the above-mentioned molten methacrylic resin (A1) and styrene-based thermoplastic elastomer (RB2) were used.
As described above, the first resin layer (thickness: 600 μm) made of the methacrylic resin (A1) / the second resin layer (thickness: 2800 μm) made of the styrene-based thermoplastic elastomer (B1) / methacrylic. Laminated sheet (methacrylic resin laminate, total sheet thickness: 4000 μm, two first resin layers with respect to the total thickness) having a three-layer structure of a first resin layer (thickness: 600 μm) made of resin (A1). The ratio of total thickness: 30%) was obtained. Table 3 shows the composition and evaluation results of each layer of the obtained sheet.

[Comparative Example 1]
A laminated sheet having a three-layer structure (methacrylic resin laminate) was obtained in the same manner as in Example 1 except that the second resin layer material was changed to a styrene-based thermoplastic elastomer (B3). Table 3 shows the composition and evaluation results of each layer of the obtained sheet.

[Comparative Example 2]
A methacrylic resin (A1) was prepared as the first resin layer material, and a styrene-based thermoplastic elastomer (B1) was prepared as the second resin layer material.
In the same manner as in Example 1, pellets of the methacrylic resin (A1) were continuously charged into a vent-type single-screw extruder having a shaft diameter of 50 mm and melt-extruded. Similar to Example 1, pellets of the styrene-based thermoplastic elastomer (B1) were continuously charged into a vent-type single-screw extruder having a shaft diameter of 30 mm and melt-extruded.
The melted methacrylic resin (A1) and the styrene thermoplastic elastomer (B1) are introduced into a junction block, and laminated and extruded (coextruded) from a 400 mm wide multi-manifold die set at 240 ° C. to 40 ° C. The embossed roll set in 1 and the metal mirror surface roll set at 100 ° C. were pressurized and cooled to form a sheet, which was taken up at a speed of 0.3 m / min.
As described above, two layers of a first resin layer (thickness: 3550 μm) made of a methacrylic resin (A1) and a second resin layer (thickness: 450 μm) made of a styrene-based thermoplastic elastomer (B1). A laminated sheet having a structure (methacrylic resin laminate, total sheet thickness: 4000 μm, ratio of the thickness of the first resin layer to the total thickness: 89%) was obtained. Table 3 shows the composition and evaluation results of each layer of the obtained sheet.

[Comparative Example 3]
A methacrylic resin (A1) was prepared as the first resin layer material.
Pellets of methacrylic resin (A1) 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 230 ° C. and a discharge rate of 28 kg / hr. This molten methacrylic resin (A1) is extruded from a single-layer die having a width of 400 mm set at 240 ° C., and pressurized and cooled by a metal mirror surface roll set at 100 ° C. and a metal mirror surface roll set at 120 ° C. It was formed into a sheet and picked up at a speed of 0.3 m / min.
As described above, a single-layer sheet composed of only the first resin layer made of the methacrylic resin (A1) (total sheet thickness: 4000 μm, ratio of the thickness of the first resin layer to the total thickness: 100%). ) Was obtained. Table 3 shows the composition and evaluation results of each layer of the obtained single-layer sheet.

[Comparative Example 4]
A styrene-based thermoplastic elastomer (B1) was prepared as the second resin layer material.
Pellets of styrene-based thermoplastic elastomer (B1) 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 130 to 210 ° C. and a discharge rate of 28 kg / hr. This molten styrene-based thermoplastic elastomer (B1) is extruded from a single-layer die having a width of 400 mm set at 220 ° C., and pressurized and cooled by an embossing roll set at 40 ° C. and a metal mirror surface roll set at 120 ° C. It was formed into a sheet and picked up at a speed of 0.3 m / min.
As described above, a single-layer sheet composed of only the second resin layer made of the styrene-based thermoplastic elastomer (B1) (total sheet thickness: 4000 μm, ratio of the thickness of the first resin layer to the total thickness: 0%) was obtained. Table 3 shows the composition and evaluation results of each layer of the obtained sheet.

[Summary of evaluation results]
In Examples 1 to 11, dynamic viscoelasticity measurement was carried out under the condition of a frequency of 1.0 Hz with the methacrylic resin (A) and JIS-K7244-4, and the change of the loss tangent (tan δ) with respect to temperature was performed. When the data of -60 ° C. to -30 ° C. was obtained, a thermoplastic elastomer (B) having at least one peak of tangent loss (tan δ) was used. In these examples, a laminated sheet having a three-layer structure (methacrylic resin lamination) in which a first resin layer containing a methacrylic resin (A) is laminated on both sides of a second resin layer containing a thermoplastic elastomer (B). Body) got. All of the laminated sheets (methacrylic resin laminated bodies) obtained in these examples were excellent in transparency, rigidity, durability, and impact resistance, and had anti-scattering properties in a wide temperature range.

From the comparison of Examples 1, 3, 4, 5, 6 or the comparison of Examples 2 and 7, by adding an appropriate amount of a methacrylic resin having an appropriate molecular weight to the second resin layer containing the thermoplastic elastomer (B). , It was found that the transparency of the laminated sheet (methacrylic resin laminated body) can be improved. The addition of an excessive amount of methacrylic resin or the addition of a high molecular weight methacrylic resin to the second resin layer may relatively reduce the transparency of the laminated sheet (methacrylic resin laminated body).

From the comparison of Examples 4, 8 and 9, by adding the multilayer structure rubber particles (C) to the first resin layer containing the methacrylic resin (A), the impact resistance of the laminated sheet (methacrylic resin laminated body) is obtained. It turned out that the sex can be improved. However, excessive addition of the multilayer structure rubber particles (C) may reduce the durability of the laminated sheet (methacrylic resin laminate).
From the comparison of Examples 1, 10 and 11, it was found that the larger the ratio of the total thickness of the two first resin layers to the total sheet thickness, the higher the rigidity of the laminated sheet (methacrylic resin laminated body). ..

In Comparative Example 1 in which a thermoplastic elastomer (B3) having no peak loss tangent (tan δ) in the temperature range of -60 to -30 ° C was used as the second resin layer material, the obtained laminated sheet (methacrylic) was used. The resin laminate) was poor in rigidity, anti-scattering property at low temperature, and anti-scattering property at room temperature.
In Comparative Example 2 in which a laminated sheet (methacrylic resin laminate) having a two-layer structure of a first resin layer / a second resin layer was produced, the obtained methacrylic resin laminate had poor durability.
In Comparative Example 3 in which a single-layer sheet composed of only the first resin layer was produced, the obtained single-layer sheet was poor in anti-scattering property at low temperature, anti-scattering property at room temperature, and impact resistance.
In Comparative Example 4 in which a single-layer sheet composed of only the second resin layer was produced, the obtained single-layer sheet had poor rigidity.

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

10 Methacrylic resin laminate 11 First resin layer 12 Second resin layer

Claims (11)

The first resin layer containing the methacrylic resin (A) includes a polymer block (b-1) containing an aromatic vinyl monomer unit and a polymer block (b-2) containing a conjugated diene monomer unit. It has a laminated structure laminated on both sides of a second resin layer containing a block copolymer containing the block copolymer or a thermoplastic elastomer (B) which is a hydrogenated additive of the block copolymer.
When the thermoplastic elastomer (B) was subjected to dynamic viscoelasticity measurement under the condition of a frequency of 1.0 Hz in accordance with JIS-K7244-4 and the data of the change in loss tangent (tan δ) with respect to temperature was acquired, the data was obtained. A methacrylic resin laminate having at least one loss tangent (tan δ) peak in the temperature range of −60 to −30 ° C. The methacrylic resin laminate according to claim 1, wherein the polymer block (b-1) contains an α-methylstyrene monomer unit as the aromatic vinyl monomer unit. When the impact test was carried out under the conditions of an environmental temperature of -40 ° C and an impact fracture energy value of 0.245 J in accordance with JIS-K7211-1, the number of fragments separated from the methacrylic resin laminate was 0. , The methacrylic resin laminate according to claim 1 or 2. The methacrylic according to any one of claims 1 to 3, wherein the first resin layer contains 95 to 60% by mass of the methacrylic resin (A) and 5 to 40% by mass of the multilayer structure rubber particles (C). Based resin laminate. The methacrylic-based resin according to any one of claims 1 to 4, wherein the second resin layer contains 95 to 60% by mass of the thermoplastic elastomer (B) and 5 to 40% by mass of the methacrylic resin (D). Resin laminate. The methacrylic resin (D) has a weight average molecular weight of 80,000 or less, and contains 80% by mass or more of a methyl methacrylate monomer unit and 5% by mass or more of a methyl acrylate monomer unit, according to claim 5. The methacrylic resin laminate according to the above. The methacrylic resin laminate according to any one of claims 1 to 6, wherein the ratio of the total thickness of the first resin layer to the total thickness is 50% or more. The methacrylic resin laminate according to any one of claims 1 to 7, which has a flexural modulus of 1500 MPa or more. Glazing for a mobile body, which comprises the methacrylic resin laminate according to any one of claims 1 to 8. A machine cover comprising the methacrylic resin laminate according to any one of claims 1 to 8. A translucent sound insulating plate containing the methacrylic resin laminate according to any one of claims 1 to 8.

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