JP2013188877A - Resin laminate and method of manufacturing the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a resin laminate having impact resistance to prevent broken pieces formed by a strong impact from scattering, as well as excellent transparency and visibility, and to provide a manufacturing method thereof.SOLUTION: The resin laminate includes at least a transparent resin layer, a coating layer, an intermediate layer, a coating layer and a transparent resin layer, which are laminated in this order. The transparent resin layer is formed of transparent resin having a Vicat softening point of ≥60°C, which is measured by the B50 method of JIS K7206 under the conditions of a load of 50N and a programming rate of 50°C/h, and a total light transmittance of ≥70%. The coating layer is formed of a copolymer obtained by copolymerizing a monomer mixture containing 50-99 mass% of a (meth)acrylic ester, 1-50 mass% of a monomer having at least one selected from hydroxy, amino and carboxyl groups and 0-49 mass% of other monomers. The intermediate layer is formed of a cross-linked polyrotaxane.

Description

  The present invention relates to a resin laminate and a method for producing the same. More specifically, the present invention relates to a resin laminate used as a sound insulation board installed on, for example, an expressway, a main road, and the like and a manufacturing method thereof.

  Sound insulation boards installed on highways and main roads are required to have transparency and visibility in addition to impact resistance that prevents fragments from scattering when damaged by strong impact.

  As such a sound insulating plate, for example, Patent Document 1 discloses a material in which a single fiber plastic filament is embedded in a transparent resin plate. However, the sound insulating plate made of such a resin plate is not sufficient in terms of transparency and visibility since a single fiber plastic filament is embedded.

Special Table 2002-526802

  The subject of this invention is providing the resin laminated body which has the outstanding transparency and visibility, and its manufacturing method in addition to the impact resistance which a fragment does not fly easily when it receives and damages with a strong impact.

Ｒ¹はメチル基または水素原子であり、ｎは１〜２０の整数である。
（３）両表層に透明樹脂層が積層された、（１）または（２）に記載の樹脂積層体。
（４）前記透明樹脂層が、アクリル樹脂層である、（１）〜（３）のいずれかの項に記載の樹脂積層体。
（５）前記架橋ポリロタキサンが、シクロデキストリンを環状分子とするポリロタキサンまたは擬ポリロタキサンを、架橋剤を介して架橋させたものである、（１）〜（４）のいずれかの項に記載の樹脂積層体。
（６）前記シクロデキストリンの少なくとも１つの水酸基が、疎水基で修飾されている、（５）に記載の樹脂積層体。
（７）６０％以上の全光線透過率を有する、（１）〜（６）のいずれかの項に記載の樹脂積層体。
（８）少なくとも透明樹脂層、コート層、中間層、コート層および透明樹脂層が、この順に積層された樹脂積層体の製造方法であって、
ＪＩＳ Ｋ７２０６のＢ５０法により、荷重５０Ｎおよび昇温速度５０℃／時の条件で測定されたビカット軟化温度が６０℃以上であり、かつ全光線透過率が７０％以上である透明樹脂を用いて、前記透明樹脂層を形成し、
前記透明樹脂層の一方の面に、（メタ）アクリル酸エステルを５０〜９９質量％、ヒドロキシ基、アミノ基およびカルボキシル基からなる群より選択される少なくとも１種の基を有する単量体を１〜５０質量％、およびこれら以外の単量体を０〜４９質量％含有する単量体混合物を共重合させて得られる共重合体で前記コート層を形成し、
前記コート層間に架橋剤含有ポリロタキサンまたは架橋剤含有擬ポリロタキサンを介在させた後、架橋剤含有ポリロタキサンまたは架橋剤含有擬ポリロタキサンを架橋させることによって前記中間層を形成する、
ことを特徴とする樹脂積層体の製造方法。
（９）前記架橋剤含有ポリロタキサンまたは架橋剤含有擬ポリロタキサンの介在が、前記架橋剤含有ポリロタキサンまたは架橋剤含有擬ポリロタキサンを前記コート層に塗布することによって行われる、（８）に記載の製造方法。
（１０）前記架橋剤含有ポリロタキサンまたは架橋剤含有擬ポリロタキサンの介在が、前記コート層間に架橋剤含有ポリロタキサンまたは架橋剤含有擬ポリロタキサンを注液することによって行われる、（８）に記載の製造方法。
（１１）両表層が透明樹脂層となるように積層される、（８）〜（１０）のいずれかの項に記載の製造方法。
（１２）上記（１）〜（７）のいずれかの項に記載の樹脂積層体を加工して得られる、遮音板。
（１３）架橋剤含有ポリロタキサンまたは架橋剤含有擬ポリロタキサンを含む、（８）に記載の製造方法に使用するための樹脂用接着剤。 As a result of intensive studies to solve the above problems, the present inventors have found a solution means having the following configuration, and have completed the present invention.
(1) A resin laminate in which at least a transparent resin layer, a coat layer, an intermediate layer, a coat layer, and a transparent resin layer are laminated in this order,
The transparent resin layer has a Vicat softening temperature of not less than 60 ° C. and a total light transmittance of not less than 70%, measured according to JIS K7206 B50 method under conditions of a load of 50 N and a heating rate of 50 ° C./hour. A layer formed of a transparent resin,
The coating layer comprises (meth) acrylic acid ester in an amount of 50 to 99% by mass, 1 to 50% by mass of a monomer having at least one group selected from the group consisting of a hydroxy group, an amino group and a carboxyl group, And a layer formed of a copolymer obtained by copolymerizing a monomer mixture containing 0 to 49% by mass of monomers other than these,
The intermediate layer is a layer formed of a crosslinked polyrotaxane;
The resin laminated body characterized by the above-mentioned.
(2) The monomer having at least one group selected from the group consisting of the hydroxy group, amino group and carboxyl group is a compound represented by the formula (I), 2-hydroxypropyl acrylate and methacrylic acid 2 -The resin laminate according to (1), which is at least one selected from the group consisting of hydroxypropyl.

R ¹ is a methyl group or a hydrogen atom, and n is an integer of 1-20.
(3) The resin laminate according to (1) or (2), wherein a transparent resin layer is laminated on both surface layers.
(4) The resin laminate according to any one of (1) to (3), wherein the transparent resin layer is an acrylic resin layer.
(5) The resin laminate according to any one of (1) to (4), wherein the crosslinked polyrotaxane is obtained by crosslinking a polyrotaxane having a cyclodextrin as a cyclic molecule or a pseudopolyrotaxane via a crosslinking agent. body.
(6) The resin laminate according to (5), wherein at least one hydroxyl group of the cyclodextrin is modified with a hydrophobic group.
(7) The resin laminate according to any one of (1) to (6), having a total light transmittance of 60% or more.
(8) A method for producing a resin laminate in which at least a transparent resin layer, a coat layer, an intermediate layer, a coat layer, and a transparent resin layer are laminated in this order,
By using a transparent resin having a Vicat softening temperature of 60 ° C. or higher and a total light transmittance of 70% or higher, measured under conditions of a load of 50 N and a heating rate of 50 ° C./hour according to the B50 method of JIS K7206. Forming the transparent resin layer;
A monomer having at least one group selected from the group consisting of 50 to 99% by mass of a (meth) acrylic acid ester, a hydroxy group, an amino group and a carboxyl group is provided on one surface of the transparent resin layer. The coating layer is formed of a copolymer obtained by copolymerizing a monomer mixture containing ˜50 mass% and other monomers other than 0 to 49 mass%,
The intermediate layer is formed by cross-linking the cross-linking agent-containing polyrotaxane or the cross-linking agent-containing pseudo-polyrotaxane after interposing the cross-linking agent-containing polyrotaxane or the cross-linking agent-containing pseudo polyrotaxane between the coat layers.
The manufacturing method of the resin laminated body characterized by the above-mentioned.
(9) The production method according to (8), wherein the crosslinking agent-containing polyrotaxane or the crosslinking agent-containing pseudo-polyrotaxane is interposed by applying the crosslinking agent-containing polyrotaxane or the crosslinking agent-containing pseudopolyrotaxane to the coating layer.
(10) The production method according to (8), wherein the crosslinking agent-containing polyrotaxane or the crosslinking agent-containing pseudopolyrotaxane is interposed by pouring the crosslinking agent-containing polyrotaxane or the crosslinking agent-containing pseudopolyrotaxane between the coat layers.
(11) The production method according to any one of (8) to (10), wherein the two surface layers are laminated so as to be a transparent resin layer.
(12) A sound insulating plate obtained by processing the resin laminate according to any one of (1) to (7).
(13) An adhesive for resin for use in the production method according to (8), comprising a polyrotaxane containing a crosslinking agent or a pseudopolyrotaxane containing a crosslinking agent.

  The resin laminate of the present invention has the effect of having excellent transparency and visibility, in addition to impact resistance that makes it difficult for fragments to scatter even when damaged by receiving a strong impact.

  The resin laminate of the present invention has a laminated structure in which at least a transparent resin layer, a transparent resin layer, a coat layer, an intermediate layer, a coat layer, and a transparent resin layer are laminated in this order. Hereinafter, the resin laminate of the present invention will be described in detail.

(Transparent resin layer)
The transparent resin layer used in the present invention is made of acrylic resin, polystyrene resin, polycarbonate resin, cycloolefin resin, amorphous polyamide resin, fluorene resin, epoxy resin, silicone resin, triacetyl cellulose resin, fluorine resin, polyethylene. It is made of transparent resin such as terephthalate resin, methyl methacrylate-styrene copolymer resin, acrylonitrile-styrene copolymer resin, polyvinyl alcohol resin, polylactic acid resin, acrylonitrile-styrene-butadiene copolymer resin, polyethylene naphthalate resin. ing. In the present invention, among these transparent resins, the Vicat softening temperature (VST) measured under the conditions of a load of 50 N and a temperature increase rate of 50 ° C./hour by the JIS K7206 B50 method is 60 ° C. or more, and the total light A transparent resin having a transmittance of 70% or more is used. When the transparent resin has a specific VST and total light transmittance, excellent transparency and visibility are exhibited. VST is preferably 60 to 200 ° C., more preferably 60 to 150 ° C., and the total light transmittance is preferably 80% or more, more preferably 90% or more. In the present invention, the total light transmittance is a value measured in accordance with JIS 7361-1.

  In the present invention, it is preferable to use an acrylic resin as the transparent resin. Examples of the acrylic resin include acrylic ester resins and methacrylic ester resins. Among them, from the viewpoints of weather resistance, transparency, and visibility, which are difficult to deteriorate even when used outdoors for a long time, methacrylate esters. Resin is preferable, and methyl methacrylate resin is preferable among methacrylic ester resins.

  The methyl methacrylate resin is a polymer obtained by polymerizing a monomer containing 50% by mass or more of methyl methacrylate, and may be a homopolymer of methyl methacrylate or 50% by mass or more. It may be a copolymer obtained by copolymerizing a monomer containing methyl methacrylate and containing other monomer copolymerizable with 50% by mass or less of methyl methacrylate. In the case of a copolymer, the proportion of methyl methacrylate is preferably 70% by mass or more, and more preferably 90% by mass or more.

  Examples of other monomers copolymerizable with methyl methacrylate include the following compounds. These other monomers may be used alone or in combination of two or more.

  Acrylic acid alkyl ester having a chain alkyl group having 1 to 12 carbon atoms such as methyl acrylate, ethyl acrylate, lauryl acrylate, etc .; Acrylic acid alkyl ester having a cyclic alkyl group having 3 to 12 carbon atoms such as cyclohexyl acrylate Acrylic acid aryl esters having an aryl group having 6 to 12 carbon atoms such as phenyl acrylate; acrylic acid ester compounds such as acrylic acid aralkyl esters having an aralkyl group having 7 to 12 carbon atoms such as benzyl acrylate;

  Methacrylic acid alkyl ester having a C2-C12 chain alkyl group such as ethyl methacrylate and lauryl methacrylate; Methacrylic acid alkyl ester having a C3-C12 cyclic alkyl group such as cyclohexyl methacrylate; Phenyl methacrylate Methacrylic acid aryl esters having an aryl group having 6 to 12 carbon atoms such as methacrylic acid aralkyl esters having an aralkyl group having 7 to 12 carbon atoms such as benzyl methacrylate.

  Styrene, α-methylstyrene, o-methylstyrene, p-methylstyrene, o-ethylstyrene, p-ethylstyrene, α-chlorostyrene, p-chlorostyrene, p-methoxystyrene, p-aminostyrene, p-acetoxy Aromatic vinyl compounds such as styrene, sodium styrenesulfonate, α-vinylnaphthalene, sodium 1-vinylnaphthalene-4-sulfonate, 2-vinylfluorene, 2-vinylpyridine, 4-vinylpyridine.

  Vinyl cyanide compounds such as acrylonitrile, α-chloroacrylonitrile, α-methoxyacrylonitrile, methacrylonitrile, α-chloromethacrylonitrile, α-methoxymethacrylonitrile, vinylidene cyanide.

  Ethylenically unsaturated carboxylic acid hydroxyalkyl ester compounds such as hydroxyethyl acrylate, hydroxyethyl methacrylate, hydroxypropyl acrylate, hydroxypropyl methacrylate, hydroxybutyl acrylate, and hydroxybutyl methacrylate.

  Acrylamide, methacrylamide, N-butoxymethyl acrylamide, N-butoxymethyl methacrylamide, N-butoxyethyl acrylamide, N-butoxyethyl methacrylamide, N-methoxymethyl acrylamide, N-methoxymethyl methacrylamide, Nn-propoxy Methyl acrylamide, Nn-propoxymethyl methacrylamide, N-methyl acrylamide, N-methyl methacrylamide, N, N-dimethyl acrylamide, N, N-dimethyl methacrylamide, N, N-diethyl acrylamide, N, N- Ethylenically unsaturated carboxylic acid amide compounds such as diethyl methacrylamide.

  Ethylenically unsaturated acid compounds such as acrylic acid, methacrylic acid, itaconic acid, fumaric acid, maleic acid, maleic anhydride, vinyl sulfonic acid, ethylenically unsaturated carboxylic acid such as isoprene sulfonic acid, ethylenically unsaturated sulfonic acid .

  Ethylenically unsaturated sulfonate compounds such as alkyl vinyl sulfonate and alkyl isoprene sulfonate.

  Allyl alcohol, methallyl alcohol, vinyl acetate, vinyl propionate, vinyl butyrate, vinyl stearate, vinyl benzoate, allyl acetate, methallyl caproate, allyl laurate, allyl benzoate, vinyl alkylsulfonate, allyl alkylsulfonate, Ethylenically unsaturated alcohols such as vinyl arylsulfonates and ester compounds thereof.

  Ethylenically unsaturated ether compounds such as methyl vinyl ether, ethyl vinyl ether, n-propyl vinyl ether, isopropyl vinyl ether, methyl allyl ether, ethyl allyl ether.

  Ethylenically unsaturated amine compounds such as vinyldimethylamine, vinyldiethylamine, vinyldiphenylamine, allyldimethylamine, and methallyldiethylamine.

  Ethylenically unsaturated silane compounds such as vinyltriethylsilane, methylvinyldichlorosilane, dimethylallylchlorosilane, and vinyltrichlorosilane.

  Vinyl halides such as vinyl chloride, vinylidene chloride, 1,2-dichloroethylene, vinyl bromide, vinylidene bromide, 1,2-dibromoethylene.

  1,3-butadiene, 2-methyl-1,3-butadiene, 2,3-dimethyl-1,3-butadiene, 2-neopentyl-1,3-butadiene, 2-chloro-1,3-butadiene, 1, 2-dichloro-1,3-butadiene, 2,3-dichloro-1,3-butadiene, 2-bromo-1,3-butadiene, 2-cyano-1,3-butadiene, substituted linear conjugated pentadienes, linear And aliphatic conjugated diene compounds such as side complex conjugated hexadiene.

  The acrylic resin is a monomer containing 50% by mass or more of acrylic acid ester and / or methacrylic acid ester, for example, emulsion polymerization method, suspension polymerization method, bulk polymerization method, injection polymerization method (cast polymerization method), etc. It is obtained by subjecting it to the polymerization method. In addition, when using together acrylic ester and methacrylic ester, the total content should just be 50 mass% or more. Polymerization is performed using light irradiation or a polymerization initiator, and an azo initiator (for example, 2,2′-azobisisobutyronitrile, 2,2′-azobis (2,4-dimethylvaleronitrile), etc.) ), Peroxide initiators (lauroyl peroxide, benzoyl peroxide, etc.), and polymerization initiators such as redox initiators in which organic peroxides and amines are combined are preferably used. The polymerization initiator is usually used in a proportion of 0.01 to 1 part by mass, preferably 0.01 to 0.5 part by mass with respect to 100 parts by mass of the monomer constituting the acrylic resin.

  The transparent resin layer may contain various additives that are generally used in the production thereof as long as the effects of the present invention are not impaired. Examples of additives include UV absorbers (hindered amine compounds, etc.) for improving weather resistance, antioxidants (phenolic compounds, phosphorus compounds, etc.) for preventing discoloration and yellowing, and molecular weight control. Chain transfer agents (such as linear or branched alkyl mercaptan compounds such as methyl mercaptan, n-butyl mercaptan, t-butyl mercaptan, n-octyl mercaptan), rubbery polymers for imparting impact resistance, flame retardancy Examples include flame retardants for imparting, crosslinking agents, and coloring agents.

  In the present invention, when the transparent resin layer is formed of an acrylic resin, as the rubbery polymer used as an additive, a part other than the rubbery polymer of the acrylic resin and a refractive index that is substantially equivalent is used. Acrylic rubber particles are particularly preferred. The acrylic rubber particles have a layer (elastic polymer layer) made of an elastic polymer mainly composed of an acrylate ester, and may be a single layer particle made of only an elastic polymer, or an elastic polymer. It may be a particle having a multilayer structure (for example, 2 to 4 layer structure) composed of a layer and a layer made of a hard polymer (hard polymer layer). The elastic polymer part in the acrylic rubber particles preferably has an average particle diameter of 40 to 800 nm.

  Examples of the rubber-like polymer include acrylic rubber particles described in JP 2011-137712 A and JP 2011-140774 A. The rubber-like polymer is contained in a proportion of preferably 0.1 to 60% by mass, more preferably 5 to 25% by mass with respect to the total amount of the monomer and the rubber-like polymer constituting the transparent resin. The rubbery polymer may be used alone or in combination of two or more.

  In this invention, it is preferable to use a flame retardant as an additive added to a transparent resin layer at the point which can provide a flame retardance. The flame retardant is not particularly limited as long as it does not inhibit the transparency of the transparent resin layer, and examples thereof include phosphate esters, silicones, halogen compounds, and inorganic compounds. It is preferable to contain the phosphate ester in at least one acrylic resin of the upper and lower surfaces of the resin laminate. Since phosphoric acid ester is particularly excellent in compatibility with acrylic resin, when acrylic resin is used as the transparent resin, flame retardancy can be imparted while maintaining the transparency of the acrylic resin layer. Moreover, although there exists a possibility that an acrylic resin layer may harden | cure depending on a flame retardant, hardening of an acrylic resin can also be suppressed by employ | adopting phosphate ester.

  Examples of phosphate esters include halogenated phosphate esters, trimethyl phosphate, triethyl phosphate, tributyl phosphate, trioctyl phosphate, tributoxyethyl phosphate, triphenyl phosphate, tricresyl phosphate, octyl diphenyl phosphate, aromatic polyphosphate, and the like. These may be used alone or in combination of two or more. Among these, halogenated phosphates are preferable, for example, tris (chloroethyl) phosphate, tris (chloropropyl) phosphate, tris (dichloropropyl) phosphate, tris (dibromopropyl) phosphate, bis (2,3-dibromopropyl). Phosphate esters containing halogen atoms such as -2,3-dichloropropyl phosphate and bis (chloropropyl) octyl phosphate; Polyphosphate esters containing halogen atoms such as halogenated alkyl polyphosphates (halogen-containing condensed phosphate esters) Etc. Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom, and a chlorinated alkyl polyphosphate in which the halogen atom is chlorine is particularly preferable.

  As these halogenated phosphoric acid esters, commercially available ones can be used, for example, “TMCPP”, “CRP”, “CR-504L”, “CR-570”, “DAIGUARD-540” (all large Hachi Chemical Industry Co., Ltd.).

  The phosphoric acid ester is contained in a proportion of 0.1 to 30% by mass, preferably 5 to 20% by mass, based on the total amount of monomers and phosphoric acid ester constituting the acrylic resin. If the phosphate ester content is too low, sufficient flame retardancy may not be obtained. Moreover, when there is too much content of phosphate ester, heat resistance may fall.

  Further, instead of using a flame retardant, a flame retardant monomer may be used in the synthesis of a transparent resin such as an acrylic resin. Examples of such a flame retardant monomer include halogenated phenyl mono (meth) acrylate and halogenated styrene. Only one type of flame retardant monomer may be used, or two or more types may be used in combination.

  In the present invention, examples of the crosslinking agent used as an additive for the transparent resin layer include compounds having a plurality of polymerizable unsaturated bonds in the molecule. By using a crosslinking agent, the surface hardness, solvent resistance and flame retardancy of the transparent resin are improved. The crosslinking agent is preferably used in a proportion of 20 parts by mass or less with respect to 100 parts by mass of the monomer constituting the transparent resin. In addition, the degree of crosslinking in the transparent resin can be represented by, for example, the degree of swelling with respect to chloroform. As the crosslinking agent used as an additive for the transparent resin layer, those containing a plurality of polymerizable unsaturated bonds in the molecule are used. For example, ethylene glycol di (meth) acrylate, tetraethylene glycol di (meth) acrylate , Diethylene glycol di (meth) acrylate, trimethylolpropane tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, neopentyl glycol di (meth) acrylate, allyl (meth) acrylate, and divinylbenzene.

  The degree of swelling is indicated by the volume ratio (absorbed chloroform / sample before immersion) of the absorbed chloroform and the sample before immersion after the sample is immersed in chloroform for a predetermined time. Preferably, the degree of swelling is 2-8.

(Coat layer)
The coating layer used in the present invention comprises a monomer having at least one group selected from the group consisting of 50 to 99% by mass of a (meth) acrylic acid ester, a hydroxy group, an amino group, and a carboxyl group. 50% by mass, and 0 to 49% by mass of monomers other than these (provided that (meth) acrylic acid ester and at least one group selected from the group consisting of a hydroxy group, an amino group and a carboxyl group) It is a layer formed of a copolymer obtained by copolymerizing a monomer mixture containing a monomer and a monomer other than these (100% by mass).
Preferably, the coat layer contains 60 to 95% by mass of (meth) acrylic acid ester and 5 to 40% by mass of a monomer having at least one group selected from the group consisting of a hydroxy group, an amino group and a carboxyl group. %, And a layer formed of a copolymer obtained by copolymerizing a monomer mixture containing 0 to 20% by mass of other monomers.

Examples of the (meth) acrylic acid ester include a (meth) acrylic acid ester having one radical polymerizable double bond or a (meth) acrylic acid ester having two or more radical polymerizable double bonds. As (meth) acrylic acid ester having one radically polymerizable double bond, acrylic acid alkyl ester having a chain alkyl group having 1 to 12 carbon atoms such as methyl acrylate, ethyl acrylate, lauryl acrylate, etc .; Acrylic acid alkyl ester having a C3-C12 cyclic alkyl group such as cyclohexyl acrylate; Acrylic acid aryl ester having a C6-C12 aryl group such as phenyl acrylate; C7-carbon such as benzyl acrylate Acrylic ester compounds such as acrylic acid aralkyl esters having 12 aralkyl groups; and methacrylic acid alkyl esters having a chain alkyl group having 1 to 12 carbon atoms such as methyl methacrylate, ethyl methacrylate, lauryl methacrylate; Cyclohexyl Methacrylic acid alkyl ester having a cyclic alkyl group having 3 to 12 carbon atoms such as methacrylic acid aryl ester having an aryl group having 6 to 12 carbon atoms such as phenyl methacrylate; aralkyl having 7 to 12 carbon atoms such as benzyl methacrylate And methacrylic acid ester compounds such as methacrylic acid aralkyl esters having a group. Among these, methyl methacrylate is preferable.
Examples of the (meth) acrylic acid ester having two or more double bonds capable of radical polymerization include polyfunctional (meth) acrylic acid esters having about 2 to 8 polymerizable groups. Examples of the bifunctional (meth) acrylic acid ester include ethylene glycol di (meth) acrylate, 1,2-propylene glycol di (meth) acrylate, 1,3-propylene glycol di (meth) acrylate, and butanediol di (meta). ) Acrylate, neopentyl glycol di (meth) acrylate, hexanediol di (meth) acrylate and other alkylene glycol di (meth) acrylate; diethylene glycol di (meth) acrylate, dipropylene glycol di (meth) acrylate, triethylene glycol di ( (Poly) oxyalkylene glycol di (meth) acrylate such as (meth) acrylate, tetraethylene glycol di (meth) acrylate, polyoxytetramethylene glycol di (meth) acrylate DOO; tricyclodecane dimethanol (meth) acrylate, di (meth) acrylate having a crosslinked cyclic hydrocarbon group such as adamantane di (meth) acrylate.
Examples of the 3- to 8-functional (meth) acrylic acid ester include glycerin tri (meth) acrylate, trimethylolpropane tri (meth) acrylate, trimethylolethane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, and pentaerythritol. Examples include tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, and dipentaerythritol hexa (meth) acrylate.
Other (meth) acrylic acid esters include, for example, polyester (meth) acrylate (for example, aliphatic polyester type (meth) acrylate, aromatic polyester type (meth) acrylate, etc.), (poly) urethane (meth) Examples include acrylate (polyester type urethane (meth) acrylate, polyether type urethane (meth) acrylate, etc.), silicone (meth) acrylate, and the like.
Such (meth) acrylic acid ester may be used independently and may use 2 or more types together.

  As the monomer having a hydroxy group, a compound represented by the following formula (I), 2-hydroxypropyl acrylate, 2-hydroxypropyl methacrylate, ethylenically unsaturated alcohol (for example, allyl alcohol, methallyl alcohol, etc.) ), A monomer having two or more double bonds capable of radical polymerization and having a hydroxy group.

Ｒ¹はメチル基または水素原子であり、ｎは１〜２０の整数である。

R ¹ is a methyl group or a hydrogen atom, and n is an integer of 1-20.

Examples of the compound represented by the formula (I) include 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, 3-hydroxypropyl acrylate, 3-hydroxypropyl methacrylate, 4-hydroxybutyl acrylate, 4-methacrylic acid 4- Examples include hydroxybutyl.
As monomers having two or more double bonds capable of radical polymerization and having a hydroxy group, 2-hydroxy-3-acryloyloxypropyl methacrylate, pentaerythritol triacrylate, pentaerythritol diacrylate, glycerin dimethacrylate And epoxy (meth) acrylate (bisphenol A type epoxy (meth) acrylate, novolac type epoxy (meth) acrylate, etc.) and the like. Among these, pentaerythritol triacrylate is preferable.

  Examples of the monomer having an amino group include ethylenically unsaturated amine compounds such as vinyldimethylamine, vinyldiethylamine, vinyldiphenylamine, allyldimethylamine, methallyldiethylamine; acrylamide, methacrylamide, N-butoxymethylacrylamide, N-butoxy Methylmethacrylamide, N-butoxyethylacrylamide, N-butoxyethylmethacrylamide, N-methoxymethylacrylamide, N-methoxymethylmethacrylamide, Nn-propoxymethylacrylamide, Nn-propoxymethylmethacrylamide, N -Methylacrylamide, N-methylmethacrylamide, N, N-dimethylacrylamide, N, N-dimethylmethacrylamide, N, N-diethylacrylamide, N Such as ethylenically unsaturated carboxylic acid amide compounds such as N- diethyl methacrylamide.

  Examples of the monomer having a carboxyl group include ethylenically unsaturated carboxylic acids such as acrylic acid, methacrylic acid, itaconic acid, fumaric acid and maleic acid.

  Such a monomer may be used independently and may use 2 or more types together. Among these, a monomer having a hydroxy group is preferable, a compound represented by formula (I), 2-hydroxypropyl acrylate or 2-hydroxypropyl methacrylate is more preferable, and a compound represented by formula (I) is further included. preferable. Among the compounds represented by the formula (I), 2-hydroxyethyl acrylate or 2-hydroxyethyl methacrylate is preferable, and 2-hydroxyethyl methacrylate is more preferable.

  The monomer mixture as a raw material for the copolymer forming the coating layer may further contain other monomers.

Other monomers should just be a monomer which has the double bond in which a radical polymerization is possible in a molecule | numerator, For example, the following monomers are mentioned.
Styrene, α-methylstyrene, o-methylstyrene, p-methylstyrene, o-ethylstyrene, p-ethylstyrene, α-chlorostyrene, p-chlorostyrene, p-methoxystyrene, p-aminostyrene, p-acetoxy Aromatic vinyl compounds such as styrene, sodium styrenesulfonate, α-vinylnaphthalene, sodium 1-vinylnaphthalene-4-sulfonate, 2-vinylfluorene, 2-vinylpyridine, 4-vinylpyridine, divinylbenzene, and the like.
Vinyl cyanide compounds such as acrylonitrile, α-chloroacrylonitrile, α-methoxyacrylonitrile, methacrylonitrile, α-chloromethacrylonitrile, α-methoxymethacrylonitrile, vinylidene cyanide.
Maleic anhydride, vinyl sulfonic acid, isoprene sulfonic acid.
Ethylenically unsaturated sulfonate compounds such as alkyl vinyl sulfonate and alkyl isoprene sulfonate.
Vinyl acetate, vinyl propionate, vinyl butyrate, vinyl stearate, vinyl benzoate, allyl acetate, methallyl caproate, allyl laurate, allyl benzoate and the like.
Vinyl alkyl sulfonate, allyl alkyl sulfonate, vinyl aryl sulfonate, etc.
Ethylenically unsaturated ether compounds such as methyl vinyl ether, ethyl vinyl ether, n-propyl vinyl ether, isopropyl vinyl ether, methyl allyl ether, ethyl allyl ether.
Ethylenically unsaturated silane compounds such as vinyltriethylsilane, methylvinyldichlorosilane, dimethylallylchlorosilane, and vinyltrichlorosilane.
Vinyl halides such as vinyl chloride, vinylidene chloride, 1,2-dichloroethylene, vinyl bromide, vinylidene bromide, 1,2-dibromoethylene.
1,3-butadiene, 2-methyl-1,3-butadiene, 2,3-dimethyl-1,3-butadiene, 2-neopentyl-1,3-butadiene, 2-chloro-1,3-butadiene, 1, 2-dichloro-1,3-butadiene, 2,3-dichloro-1,3-butadiene, 2-bromo-1,3-butadiene, 2-cyano-1,3-butadiene, substituted linear conjugated pentadienes, linear and Aliphatic conjugated diene compounds such as side complex conjugated hexadiene.

  Such other monomers may be used alone or in combination of two or more.

  The coating layer is prepared by dissolving a copolymer obtained by copolymerizing a monomer mixture in a solvent and applying the copolymer solution to remove the solvent. For example, a partially reacted prepolymer is applied and polymerized by heat or light irradiation. Examples of the solvent include methanol, ethanol, 1-propanol, 2-propanol (isopropyl alcohol), 1-butanol, 2-butanol (sec-butyl alcohol), 2-methyl-1-propanol (isobutyl alcohol), 2- Alcohols such as methyl-2-propanol (tert-butyl alcohol); 2-ethoxyethanol, 2-butoxyethanol, 3-methoxy-1-propanol, 1-methoxy-2-propanol, 1-ethoxy-2-propanol Alkoxy alcohols such as diacetone alcohol; ketones such as acetone, methyl ethyl ketone and methyl isobutyl ketone; aromatic hydrocarbons such as toluene and xylene; esters such as ethyl acetate and butyl acetate Kind, and the like. Such a solvent may be used independently and may use 2 or more types together. Moreover, the polymerization by light irradiation is suitably performed by irradiating activation energy rays. Examples of the activation energy rays include electron beams, ultraviolet rays, and visible rays, and are appropriately selected according to the composition of the monomer mixture.

Furthermore, the monomer mixture may contain the polymerization initiator and additive described in the description of the transparent resin layer. When the polymerization is carried out by light irradiation using ultraviolet rays or visible rays as the activation energy rays, a photopolymerization initiator is usually used.
Examples of the photopolymerization initiator include acetophenone, acetophenone benzyl ketal, anthraquinone, 1- (4-isopropylphenyl) -2-hydroxy-2-methylpropan-1-one, carbazole, xanthone, 4-chlorobenzophenone, 4, 4′-diaminobenzophenone, 2,2-dimethoxy-1,2-diphenylethane-1-one, 3,3′-dimethyl-4-methoxybenzophenone, thioxanthone, 2,2-dimethoxy-2-phenylacetophenone, 1- (4-dodecylphenyl) -2-hydroxy-2-methylpropan-1-one, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropan-1-one, triphenylamine, 2 , 4,6-Trimethylbenzoyldiphenylphosphine oxide 1-hydroxycyclohexyl phenyl ketone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, fluorenone, fluorene, benzaldehyde, benzoin ethyl ether, benzoin propyl ether, benzophenone, Michler ketone, 3-methylacetophenone, 3, 3 ′, 4,4′-tetra-tert-butylperoxycarbonylbenzophenone (BTTB), 2- (dimethylamino) -1- [4- (morpholinyl) phenyl] -2- (phenylmethyl) -1-butanone, 4-Benzoyl-4′-methylphenyl sulfide, benzyl, 1- [4- (2-hydroxyethoxy) -phenyl] -2-hydroxy-2-methyl-1-propan-1-one, 2-benzyl-2- Dimethylamino-1- (4-morpho Linophenyl) -butanone-1, bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide, bis (η5-2,4-cyclopentadien-1-yl) -bis (2,6-difluoro-3- ( 1H-pyrrol-1-yl) -phenyl) titanium and the like.
A commercial item can be used for these photoinitiators. Examples of commercially available products include “IRGACURE 651”, “IRGACURE 184”, “IRGACURE 500”, “IRGACURE 1000”, “IRGACURE 2959”, “DAROCUR 1173”, “IRGACURE 907”, “IRGACURE 369”, “IRGACURE 369”, “IRGACURE 369”, “IRGACURE 369”, “IRGACURE 369” ”,“ IRGACURE 1800 ”,“ IRGACURE 819 ”,“ IRGACURE 784 ”,“ LUCIRIN TPO ”(above, manufactured by BASF),“ KAYACURE ITX ”,“ KAYACURE DETX-S ”,“ KAYACURE BP-100 ”,“ KAYACURE BP-100 ” “KAYACURE BMS”, “KAYACURE 2-EAQ” (manufactured by Nippon Kayaku Co., Ltd.) and the like.
A photoinitiator may be used independently and may use 2 or more types together. When using a photoinitiator, the usage-amount is 0.1-5 mass parts normally with respect to a total of 100 mass parts of all the monomers in a monomer mixture. Moreover, the intensity | strength and irradiation time of an activation energy ray are suitably adjusted according to the composition of a monomer mixture, the thickness of a coating layer, etc. The activation energy ray may be irradiated in an inert gas (for example, nitrogen, argon, etc.) atmosphere.

By having the coat layer, the resin laminate of the present invention reacts with the crosslinking agent contained in the intermediate layer, when the intermediate layer described later is crosslinked, the functional group present in the copolymer forming the coat layer. Therefore, the coat layer and the intermediate layer are chemically bonded to each other, so that interface peeling can be prevented and impact resistance can be improved.
In addition, it is possible to introduce a functional group into the polymer forming the transparent resin layer without causing the coat layer to be chemically bonded to the intermediate layer, but such a reactive functional group is hydrophilic. Therefore, it is considered that the water absorption of the transparent resin layer increases and the deterioration with time is likely to occur. By providing the coat layer, the above effects can be obtained without impairing the performance of the transparent resin layer.

(Middle layer)
The intermediate layer used in the present invention is a layer formed of a crosslinked polyrotaxane or a pseudopolyrotaxane.

  A “rotaxane” is a compound in which a chain molecule (rod-like molecule) penetrates through the ring part of the cyclic molecule. Usually, both of the chain molecules are prevented so that the cyclic molecule is not detached from the chain molecule. A blocking group is bonded to the terminal and serves as a stopper. In addition, “polyrotaxane” refers to a rotaxane in which a chain molecule penetrates the ring portion of a plurality of cyclic molecules, and “pseudopolyrotaxane” refers to both ends of the polyrotaxane chain molecule being blocked by a blocking group. It refers to polyrotaxane that has not been used.

  The polyrotaxane or pseudopolyrotaxane used as the raw material for the crosslinked polyrotaxane is not particularly limited, but it is preferable to use a polyrotaxane in that the cyclic molecules are not easily detached. Examples of the cyclic molecule include cyclodextrin, crown ether, cyclophane, calixarene, and cyclic amide. In addition, the chain molecule is substantially linear, and the length thereof is not particularly limited, and the chain molecule may have a branched chain as long as the cyclic molecule as a rotor is rotatable.

  As the cyclic molecule, cyclodextrin is preferable. For example, α-cyclodextrin (6 glucose), β-cyclodextrin (7 glucose), γ-cyclodextrin (8 glucose), dimethylcyclodextrin, glucosylcyclodextrin, these And derivatives thereof. In addition, the same cyclic molecule (for example, only α-cyclodextrin) may be pierced in one chain molecule, or different cyclic molecules (for example, α-cyclodextrin and β-cyclodextrin) may be pierced. You may do it.

  Furthermore, when the cyclic molecule is cyclodextrin, it is preferable that at least one hydroxyl group of cyclodextrin is modified with a hydrophobic group. By modifying a part of the hydroxyl group that is a hydrophilic group with a hydrophobic group, the solubility in an organic solvent can be increased. The ratio of the hydroxyl group modified with a hydrophobic group (modification rate) is preferably 2% or more, more preferably 10% or more when the modification rate when all hydroxyl groups of cyclodextrin are modified with a hydrophobic group is 100%. is there. Examples of the hydrophobic group include an alkyl group, a benzyl group, a benzene derivative-containing group, an acyl group, a silyl group, a trityl group, a urethane bond, an ester bond, and an ether bond. When modifying a plurality of hydroxyl groups, it may be modified not only with a single hydrophobic group but also with two or more hydrophobic groups.

  The chain molecule is not particularly limited, and examples thereof include polyesters such as polyalkylenes and polycaprolactone, polyethers such as polyethylene glycol, polyamides, acrylic resins, and linear compounds having a benzene ring. Among these, polyethylene glycol and polycaprolactone are preferable.

  The chain molecule preferably has a weight average molecular weight of 1,000 to 500,000, more preferably 10,000 to 300,000, and still more preferably 10,000 to 100,000.

  In the polyrotaxane, a blocking group is bonded to both ends of the chain molecule in order to make it difficult for the cyclic molecule to be detached. Examples of the blocking group include various groups including molecular groups and polymer groups having bulkiness and ionicity.

  Examples of the bulky group include a spherical group and a side wall-shaped group. Further, in the case of an ionic group, the ionicity of the ionic group and the ionicity of the cyclic molecule influence each other, and, for example, repel each other, thereby preventing the detachment of the cyclic molecule. . Specific examples of the blocking group include dinitrophenyl groups (2,4-dinitrophenyl group, 3,5-dinitrophenyl group, etc.), dialkylphenyl groups, cyclodextrins, adamantane groups, trityl groups, Examples include fluoresceins, pyrenes, derivatives or modified products thereof.

  In the present invention, the crosslinked polyrotaxane forming the intermediate layer is a crosslinked product of the above-mentioned polyrotaxane or pseudopolyrotaxane. The crosslinked polyrotaxane is obtained by mixing a polyrotaxane or a pseudopolyrotaxane with a crosslinking agent, and chemically and / or physically combining the polyrotaxanes in the obtained crosslinking agent-containing polyrotaxane or the obtained pseudopolyrotaxanes in the crosslinking agent-containing pseudopolyrotaxane. It is obtained by crosslinking, preferably chemical crosslinking.

  The crosslinking agent is not particularly limited, and is a polyisocyanate compound having a plurality of isocyanate groups in one molecule, a blocked polyisocyanate compound having a plurality of blocked isocyanate groups in one molecule, and having a plurality of hydroxyl groups in one molecule. Examples thereof include a polyol compound and a polycarboxylic acid compound having a plurality of carboxyl groups in one molecule. In addition, as a crosslinking agent, a compound obtained by reacting a polyisocyanate compound and a polyol compound, or a block polyisocyanate compound obtained by protecting the isocyanate group of a compound obtained by reacting a polyisocyanate compound and a polyol compound with a blocking agent It can be used.

  Examples of the polyisocyanate compound include aromatic polyisocyanate, aliphatic polyisocyanate, and alicyclic polyisocyanate. Examples of the aromatic polyisocyanate include 4,4′-diphenylmethane diisocyanate, 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, naphthalene-1,5-diisocyanate, o-xylylene diisocyanate, and m-xylylene. Examples include range isocyanate and 2,4-tolylene dimer. Examples of the aliphatic polyisocyanate include tetramethylene diisocyanate, hexamethylene diisocyanate, methylene diisocyanate, and trimethylhexamethylene diisocyanate. Examples of the alicyclic polyisocyanate include bicycloheptane triisocyanate, 4,4′-methylenebis (cyclohexyl isocyanate), isophorone diisocyanate, 1,3-bis (isocyanatomethyl) cyclohexane, and the like. A polyisocyanate compound may be used independently and may use 2 or more types together as needed. Moreover, an adduct body, a biuret body, an isocyanurate body, etc. can be used for a polyisocyanate compound.

  The blocked polyisocyanate compound is a compound having a plurality of blocked isocyanate groups in which isocyanate groups are protected by reaction with a blocking agent and temporarily inactivated. The blocking agent can be dissociated when heated to a predetermined temperature. As such a block polyisocyanate compound, an addition reaction product of a polyisocyanate compound and a blocking agent is used. Examples of the polyisocyanate compound that can react with the blocking agent include isocyanurate bodies, biuret bodies, and adduct bodies. As this polyisocyanate compound, the compound illustrated as the above-mentioned polyisocyanate compound is mentioned. A block polyisocyanate compound may be used independently and may use 2 or more types together as needed.

  Examples of the blocking agent include phenolic blocking agents such as phenol, cresol, xylenol, chlorophenol, and ethylphenol; lactam blocking agents such as ε-caprolactam, δ-valerolactam, γ-butyrolactam, and β-propiolactam; Active methylene blocking agents such as ethyl acetoacetate and acetylacetone; methanol, ethanol, propanol, butanol, amyl alcohol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, propylene glycol monomethyl ether, benzyl Ether, methyl glycolate, butyl glycolate, diacetone alcohol, methyl lactate, ethyl lactate Any alcohol blocking agent; oxime blocking agent such as formaldehyde oxime, acetaldoxime, acetoxime, methyl ethyl ketoxime, diacetyl monooxime, cyclohexanone oxime; butyl mercaptan, hexyl mercaptan, t-butyl mercaptan, thiophenol, methylthiophenol, ethylthio Mercaptan block agents such as phenol; acid amide block agents such as acetamide and benzamide; imide block agents such as succinimide and maleic imide; amine block agents such as xylidine, aniline, butylamine and dibutylamine; imidazole, Examples include imidazole blocking agents such as 2-ethylimidazole; imine blocking agents such as methyleneimine and propyleneimine. It is done. A blocking agent may be used independently and may use 2 or more types together as needed.

  A commercially available block polyisocyanate compound may be used, for example, Sumidur BL-3175, BL-4165, BL-1100, BL-1265, Desmodur TPLS-2957, TPLS-2062, TPLS-2078, TPLS. -2117, desmotherm 2170, desmotherm 2265 (above, manufactured by Sumitomo Bayer Urethane Co., Ltd.), coronate 2512, coronate 2513, coronate 2520 (above, manufactured by Nippon Polyurethane Industry Co., Ltd.), B-830, B-815, B- 846, B-870, B-874, B-882 (Mitsui Takeda Chemical Co., Ltd.), TPA-B80E, 17B-60PX, E402-B80T (Asahi Kasei Chemicals Co., Ltd.), and the like. . Sumidu BL-3175 and BL-4165 are those using methyl ethyl ketoxime as a blocking agent.

  Examples of the polyol compound include polyester polyol, polyester amide polyol, polyether polyol, polyether ester polyol, polycarbonate polyol, and polyolefin polyol. A polyol compound may be used independently and may use 2 or more types together as needed.

  Examples of the polycarboxylic acid compound include aromatic polycarboxylic acid and aliphatic polycarboxylic acid. A polycarboxylic acid compound may be used independently and may use 2 or more types together as needed.

  Furthermore, a catalyst can be used to accelerate the crosslinking reaction. When a polyisocyanate compound or a block polyisocyanate compound is used as the crosslinking agent, examples of the catalyst include a tin compound, a metal chloride, a metal acetylacetonate salt, a metal sulfate, and an amine compound. These catalysts may be used independently and may use 2 or more types together as needed. When a polyol compound or a polycarboxylic acid compound is used as the crosslinking agent, examples of the catalyst include alkali metal compounds, tin compounds, titanium compounds, and p-toluenesulfonic acid. These catalysts may be used independently and may use 2 or more types together as needed.

(Resin laminate)
As described above, the resin laminate of the present invention has a laminated structure in which at least a transparent resin layer, a coat layer, an intermediate layer, a coat layer, and a transparent resin layer are laminated in this order. The resin laminate of the present invention preferably has a transparent resin layer laminated on both surface layers. In addition, the number of layers is not particularly limited as long as it has a structure of “transparent resin layer, coat layer, intermediate layer, coat layer, and transparent resin layer”. Layer / coat layer / intermediate layer / coat layer / transparent resin layer / coat layer / intermediate layer / coat layer / transparent resin layer) or a layered structure of more than this.
Considering the transparency and thickness of the resin laminate, a five-layer structure (transparent resin layer / coat layer / intermediate layer / coat layer / transparent resin layer) is preferable.

When the resin laminate of the present invention has a five-layer structure, the two transparent resin layers may be formed of the same transparent resin, or may be formed of different transparent resins. The transparent resin layer preferably has a thickness of 1 to 15 mm, more preferably 2 to 10 mm. The thickness of the transparent resin layer is appropriately set according to the use of the resin laminate, and the two layers may have the same thickness or different thicknesses.
The two coat layers may be formed of the same copolymer or may be formed of different copolymers. The coat layer preferably has a thickness of 0.5 to 100 μm, more preferably 1 to 30 μm. The thickness of the coat layer is appropriately set according to the use of the resin laminate, and the two layers may have the same thickness or different thicknesses.
The intermediate layer preferably has a thickness of 0.1 to 8 mm, more preferably 0.5 to 4 mm.

  The thickness of the resin laminate of the present invention is not particularly limited as long as it does not impair the moldability and transparency of a molded product such as a sound insulation board. Usually, it is about 2 to 38 mm, preferably about 5 to 30 mm. Furthermore, the resin laminate of the present invention preferably has a total light transmittance of 60% or more, more preferably 70% or more.

(Method for producing resin laminate)
The production method of the resin laminate of the present invention is not particularly limited as long as at least a transparent resin layer, a coat layer, an intermediate layer, a coat layer, and a transparent resin layer can be produced in this order. For example, both surface layers are transparent. It is preferable to laminate so as to be a resin layer. The resin laminate of the present invention has a Vicat softening temperature of 60 ° C. or higher and a total light transmittance of 70% or higher measured according to JIS K7206 B50 method under conditions of a load of 50 N and a heating rate of 50 ° C./hour. A transparent resin layer is formed using a transparent resin, and (meth) acrylic acid ester is selected from the group consisting of 50 to 99% by mass, a hydroxy group, an amino group, and a carboxyl group on one surface of the transparent resin layer. Coat layer with a copolymer obtained by copolymerizing a monomer mixture containing 1 to 50% by mass of a monomer having at least one group and 0 to 49% by mass of other monomers And a crosslinker-containing polyrotaxane or a crosslinker-containing pseudopolyrotaxane is interposed between the coat layers, and then the crosslinker-containing polyrotaxane or the crosslinker-containing pseudopolyrotaxane is cross-linked. To obtain an intermediate layer.

Examples of the method of interposing the crosslinking agent-containing polyrotaxane or the crosslinking agent-containing pseudopolyrotaxane include the following method (A) or (B).
(A) A method of applying a crosslinking agent-containing polyrotaxane or a crosslinking agent-containing pseudopolyrotaxane to a coating layer.
(B) A method in which a crosslinking agent-containing polyrotaxane or a crosslinking agent-containing pseudopolyrotaxane is injected between coat layers.

  In the method (A), first, a crosslinker-containing polyrotaxane or a crosslinker-containing pseudopolyrotaxane is applied to one coat layer (film) so as to have a desired thickness, and another coat layer is placed thereon. Is the method.

  The crosslinker-containing polyrotaxane or the crosslinker-containing pseudopolyrotaxane is preferably applied to a coating layer around which a frame plate (for example, a gasket or the like) is installed. That is, it can apply | coat with uniform thickness by apply | coating to the part enclosed with the frame boards like a gasket.

  In the coating layer, a transparent resin layer may be previously laminated on the surface opposite to the surface in contact with the crosslinker-containing polyrotaxane or the crosslinker-containing pseudopolyrotaxane. The crosslinker-containing polyrotaxane or the crosslinker-containing pseudopolyrotaxane A transparent resin layer may be laminated after coating.

  In the method (B), a crosslinking agent-containing polyrotaxane or a crosslinking agent-containing pseudopolyrotaxane is injected into a cell composed of two coat layers (films) and a gasket, and the crosslinking agent-containing polyrotaxane or the crosslinking agent-containing pseudo In this method, a polyrotaxane is crosslinked to obtain a resin laminate. The layer thickness of the crosslinked polyrotaxane (intermediate layer) is adjusted by the width of the gap formed by the two coating layers. In the coating layer, a transparent resin layer may be previously laminated on the surface opposite to the surface in contact with the crosslinker-containing polyrotaxane or the crosslinker-containing pseudopolyrotaxane. The crosslinker-containing polyrotaxane or the crosslinker-containing pseudopolyrotaxane After the liquid injection, a transparent resin layer may be laminated.

In such a resin laminate having a laminate structure of five or more layers, the transparent resin layers may all be formed of the same transparent resin, or some of them may be the same and the rest may be different (for example, both The surface layer may be formed of the same transparent resin, the other transparent resin layer may be formed of another transparent resin, or the like, or each may be formed of a different transparent resin.
The coat layers may all be formed of the same copolymer, part of them may be the same and the rest may be different, or each may be formed of a different copolymer.
Similarly, all of the intermediate layers may be formed of the same crosslinked polyrotaxane, a part thereof may be the same and the rest may be different, or each may be formed of a different crosslinked polyrotaxane.

The thickness of the transparent resin layer is appropriately set according to the use of the resin laminate, and may be all the same thickness, or a part of the thickness may be the same and the rest may be different (for example, both surface layers). May be the same thickness and the other transparent resin layers may have different thicknesses), or different thicknesses.
The thickness of the coat layer is appropriately set according to the use of the resin laminate, and may all be the same thickness, or may be a part of the same thickness and the rest being different, or different thicknesses. Good.
Further, the thickness of the intermediate layer is appropriately set according to the use of the resin laminate, and may all be the same thickness, or may be partially the same thickness with the remainder being different or different. Thickness may be used.

  A resin laminate having a laminate structure of five or more layers can also be basically obtained by the same method as a resin laminate having a five-layer structure. For example, when the method (A) is employed, the application of the crosslinking agent-containing polyrotaxane or the crosslinking agent-containing pseudopolyrotaxane and the crosslinking reaction may be repeated until the desired number of layers is reached. Alternatively, a cross-linking agent-containing polyrotaxane or a cross-linking agent-containing pseudo-polyrotaxane is applied on the coat layer laminated on the transparent resin layer, a coat layer is further placed, a transparent resin layer is laminated on the coat layer, and the desired number of layers is obtained. The cross-linking agent-containing polyrotaxane or the cross-linking agent-containing pseudopolyrotaxane may be cross-linked at once.

  Moreover, when employ | adopting the method of the said (B), what is necessary is just to repeat the injection and crosslinking reaction of a crosslinking agent containing polyrotaxane or a crosslinking agent containing pseudopolyrotaxane until it becomes the desired number of layers.

  As described above, the cross-linking agent-containing polyrotaxane or the cross-linking agent-containing pseudo-polyrotaxane also exhibits a behavior as an adhesive (adhesive layer) by being interposed between the coat layer and the coat layer, and therefore, in the present invention. In the manufacturing method of the resin laminated body which concerns, it can use suitably.

  In addition to the sound insulation board, the resin laminate of the present invention can be used for applications such as a windproof board installed on the side of a bridge on which a railway vehicle or an automobile travels. When the resin laminate of the present invention is used as a sound insulation board installed on an expressway or a main road, the surface thereof may be, for example, a hard coat, water repellent finish, hydrophilic finish, photocatalytic finish, etc. Processing may be performed, and furthermore, a display for preventing bird collision may be provided.

  EXAMPLES Hereinafter, although an Example and a comparative example are given and this invention is demonstrated concretely, this invention is not limited to these Examples. In addition, the impact resistance and total light transmittance of the laminated resin plate were evaluated by the following methods.

<Impact resistance>
The obtained resin laminate was cut into a size of 150 mm × 150 mm to prepare a test piece. With the two sides of the test piece fixed, a steel ball of 3 kg from 0.85 m above the test piece was continuously dropped three times. The state of the test piece at that time was evaluated according to the following criteria.
A: Even when the steel balls were dropped three times in succession, scattering of the methyl methacrylate resin plates on the front and back of the test piece was not observed.
○: After dropping the steel ball three times in succession, scattering of the methyl methacrylate resin plates on the front and back of the test piece was recognized for the first time.
(Triangle | delta): After dropping a steel ball twice continuously, scattering of the methyl methacrylate type | system | group resin board of a test piece front and back was recognized for the first time.
X: After dropping the steel ball once, scattering of the methyl methacrylate resin plates on the front and back of the test piece was observed.

<Vicat softening temperature>
The obtained methyl methacrylate resin plate was cut into a size of 20 mm × 20 mm to prepare a test piece. The Vicat softening temperature of the obtained test piece was measured under the conditions of a load of 50 N and a heating rate of 50 ° C./hour in accordance with JIS K7206 B50 method.

<Total light transmittance>
About the obtained resin laminated board, the total light transmittance Tt was measured based on JISK7361-1 using the transmittance meter ("HR-100" by Murakami Color Research Laboratory Co., Ltd.). The larger this value, the greater the light transmission, that is, the higher the transparency.

Example 1
(Manufacture of transparent resin layer (methyl methacrylate resin plate))
87.9 parts by mass of a methyl methacrylate partial polymer syrup containing 5% by mass of polymethyl methacrylate formed by polymerization of methyl methacrylate, 0.1 part by mass of neopentyl glycol dimethacrylate, and chlorinated alkyl polyphosphate (large 0.07 parts by mass of 2,2′-azobisisobutyronitrile was added and mixed with 100 parts by mass in total of 12 parts by mass of “CR570” manufactured by Hachi Chemical Industry Co., Ltd. Next, the obtained mixture was poured into a cell having a gap of 6 mm composed of two glass plates and a soft polyvinyl chloride gasket, and in a polymerization tank using air as a heat medium at 60 ° C. Polymerization was carried out by heating for 8 hours and then at 110 ° C. for 1 hour to obtain a methyl methacrylate resin plate (Vicat softening temperature: 95 ° C., total light transmittance: 92.5%).

(Formation of coat layer)
18 mL of methyl methacrylate (MMA), 2 g of 2-hydroxyethyl methacrylate (HEMA), 0.006 g of n-octyl mercaptan, 0.002 g of 2,2′-azobisisobutyronitrile, and 80 g of ethyl acetate Mix in a separable flask. Next, the inside of the separable flask was purged with nitrogen and reacted at 70 ° C. for 8 hours while refluxing to obtain a copolymer of MMA and HEMA (MMA-co-HEMA10) as a mixture with ethyl acetate.
On the methyl methacrylate resin plate, the obtained mixture of MMA-co-HEMA 10 and ethyl acetate was applied with a glass rod with the thickness adjusted so that the thickness of the coating layer after drying was 10 μm. After coating, the methyl methacrylate resin plate coated with a mixture of MMA-co-HEMA 10 and ethyl acetate was dried at room temperature for 1 hour. Subsequently, the ethyl acetate was removed by drying in a vacuum oven at 70 ° C. for 3 hours, and a coating layer having a thickness of 10 μm was formed on the methyl methacrylate resin plate.

(Manufacture of resin laminates)
Two of the obtained coating layer-containing methyl methacrylate resin plates (thickness: about 6 mm, 200 mm × 200 mm) were dried at 90 ° C. for 12 hours under vacuum conditions. Next, a silicone gasket having a thickness of 2 mm was placed on one coated layer side of the dried methyl methacrylate resin plate, and a crosslinker-containing polyrotaxane heated to 130 ° C. was applied. As the cross-linking agent-containing polyrotaxane, Celum ^™ elastomer S-1000 (manufactured by Advanced Soft Material Co., Ltd.), which was deaerated under vacuum for 8 hours while being heated at 130 ° C., was used. Next, the surface coated with the crosslinker-containing polyrotaxane was covered with another coat layer-containing methyl methacrylate resin plate so that the coat layer was in contact with the crosslinker-containing polyrotaxane. Fix with clamp and perform crosslinking reaction at 150 ° C. for 7 hours, 5 layers of transparent resin layer (6 mm) / coat layer (10 μm) / intermediate layer (2 mm) / coat layer (10 μm) / transparent resin layer (6 mm) A resin laminate having a structure was obtained. The resulting resin laminate was evaluated for impact resistance and total light transmittance. The results are shown in Table 1.

(Example 2)
Other than using the following copolymer (MMA-co-HEMA20) as the copolymer for forming the coat layer, the intermediate layer thickness being 1 mm (that is, using a silicone gasket having a thickness of 1 mm) Is a resin laminate having a five-layer structure of transparent resin layer (6 mm) / coat layer (10 μm) / intermediate layer (1 mm) / coat layer (10 μm) / transparent resin layer (6 mm) in the same procedure as in Example 1. I got a plate. The resulting resin laminate was evaluated for impact resistance and total light transmittance. The results are shown in Table 1.

(Synthesis of MMA-co-HEMA20)
A copolymer (MMA-co-HEMA 20) was obtained in the same procedure as in Example 1 except that 16 g of methyl methacrylate (MMA) and 4 g of 2-hydroxyethyl methacrylate (HEMA) were used.

(Comparative Example 1)
Two methyl methacrylate resin plates obtained in Example 1 (production of transparent resin layer (methyl methacrylate resin plate)) were dried at 90 ° C. for 12 hours under vacuum. Next, the two methyl methacrylate resin plates were bonded with chloroform to obtain a methyl methacrylate resin laminate. The resulting methyl methacrylate resin laminate was evaluated for impact resistance and total light transmittance. The results are shown in Table 1.

As shown in Table 1, the resin laminates obtained in Examples 1 and 2 and Comparative Example 1 all had a total light transmittance of 90%. However, as for impact resistance, the resin laminates obtained in Examples 1 and 2 had no methyl methacrylate resin plate scattered even when the steel balls were dropped three times in succession. On the other hand, in the resin laminated plate obtained in Comparative Example 1, scattering of the methyl methacrylate-based resin plate was observed after dropping the steel ball once.
Furthermore, for the resin laminates obtained in Examples 1 and 2, not only was no scattering observed in the impact resistance test, but also the interface between the transparent resin layer and the coating layer after the impact resistance test, and the coating No peeling was observed at the interface between the layer and the intermediate layer. On the other hand, with respect to the resin laminate obtained in Comparative Example 1, the two methyl methacrylate resin plates were severely crushed in the impact resistance test, and the interface between the layers peeled off and was not maintained.

Claims (13)

At least a transparent resin layer, a coat layer, an intermediate layer, a coat layer and a transparent resin layer are laminated in this order,
The transparent resin layer has a Vicat softening temperature of not less than 60 ° C. and a total light transmittance of not less than 70%, measured according to JIS K7206 B50 method under conditions of a load of 50 N and a heating rate of 50 ° C./hour. A layer formed of a transparent resin,
The coating layer comprises (meth) acrylic acid ester in an amount of 50 to 99% by mass, 1 to 50% by mass of a monomer having at least one group selected from the group consisting of a hydroxy group, an amino group and a carboxyl group, And a layer formed of a copolymer obtained by copolymerizing a monomer mixture containing 0 to 49% by mass of monomers other than these,
The intermediate layer is a layer formed of a crosslinked polyrotaxane;
The resin laminated body characterized by the above-mentioned. The monomer having at least one group selected from the group consisting of the hydroxy group, amino group and carboxyl group is a compound represented by the formula (I), 2-hydroxypropyl acrylate and 2-hydroxypropyl methacrylate The resin laminate according to claim 1, which is at least one selected from the group consisting of:

R ¹ is a methyl group or a hydrogen atom, and n is an integer of 1-20.   The resin laminate according to claim 1 or 2, wherein a transparent resin layer is laminated on both surface layers.   The resin laminate according to any one of claims 1 to 3, wherein the transparent resin layer is an acrylic resin layer.   The resin laminate according to any one of claims 1 to 4, wherein the crosslinked polyrotaxane is obtained by crosslinking a polyrotaxane having a cyclodextrin as a cyclic molecule or a pseudopolyrotaxane via a crosslinking agent.   The resin laminate according to claim 5, wherein at least one hydroxyl group of the cyclodextrin is modified with a hydrophobic group.   The resin laminate according to any one of claims 1 to 6, which has a total light transmittance of 60% or more. At least a transparent resin layer, a coat layer, an intermediate layer, a coat layer and a transparent resin layer are a method for producing a resin laminate in which the layers are laminated in this order,
By using a transparent resin having a Vicat softening temperature of 60 ° C. or higher and a total light transmittance of 70% or higher, measured under conditions of a load of 50 N and a heating rate of 50 ° C./hour according to the B50 method of JIS K7206. Forming the transparent resin layer;
A monomer having at least one group selected from the group consisting of 50 to 99% by mass of a (meth) acrylic acid ester, a hydroxy group, an amino group and a carboxyl group is provided on one surface of the transparent resin layer. The coating layer is formed of a copolymer obtained by copolymerizing a monomer mixture containing ˜50 mass% and other monomers other than 0 to 49 mass%,
The intermediate layer is formed by cross-linking the cross-linking agent-containing polyrotaxane or the cross-linking agent-containing pseudo-polyrotaxane after interposing the cross-linking agent-containing polyrotaxane or the cross-linking agent-containing pseudo polyrotaxane between the coat layers.
The manufacturing method of the resin laminated body characterized by the above-mentioned.   The production method according to claim 8, wherein the crosslinking agent-containing polyrotaxane or the crosslinking agent-containing pseudopolyrotaxane is interposed by applying the crosslinking agent-containing polyrotaxane or the crosslinking agent-containing pseudopolyrotaxane to the coating layer.   The production method according to claim 8, wherein the crosslinking agent-containing polyrotaxane or the crosslinking agent-containing pseudopolyrotaxane is interposed by injecting the crosslinking agent-containing polyrotaxane or the crosslinking agent-containing pseudopolyrotaxane between the coat layers.   The manufacturing method according to any one of claims 8 to 10, wherein both surface layers are laminated so as to be transparent resin layers.   A sound insulating board obtained by processing the resin laminate according to any one of claims 1 to 7.   The adhesive agent for resin for using for the manufacturing method of Claim 8 containing a crosslinking agent containing polyrotaxane or a crosslinking agent containing pseudopolyrotaxane.