JP2018034489A - Laminate and method for producing the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a laminate which prevents blocking, has a coating layer laminated on a base material layer with good adhesiveness without subjected to surface treatment such as corona treatment, and has good bendability, and to provide a method for producing the same.SOLUTION: A laminate contains a base material layer X containing a resin selected from the group consisting of a cyclic olefin polymer, polycarbonate and polyester, and a layer Y which is provided on at least one surface of the base material layer X and is formed of a cured product of an acrylic resin composition containing 20-90 pts.mass of an acrylic resin A and 10-80 pts.mass of an acrylic monomer B, where Tg of the cured product of the acrylic resin composition is 40°C or higher and 90°C or lower.SELECTED DRAWING: None

Description

  The present invention relates to a laminate and a method for producing the same.

  Cyclic olefin polymers, polycarbonates, polyesters, and the like are suitably used as resin substrates. In particular, cyclic olefin polymers are widely used as optical materials because they have excellent transparency and heat resistance.

  On the other hand, the cyclic olefin polymer has low brittleness and is easily cracked. On the other hand, the technique which coats an acrylic resin layer etc. on the base material which contains a cyclic olefin polymer as a main component, and makes it a laminated body is proposed (for example, patent document 1).

Japanese Patent Laid-Open No. 2005-2176

  However, in order to coat a polar resin on a base material containing a cyclic olefin polymer as a main component, a surface treatment such as a corona treatment is required, resulting in an increase in the lamination process and cost.

  Moreover, when coating a resin layer on a base material, it is calculated | required that a blocking (surface stickiness) does not arise.

  The present invention has been made in view of the above circumstances, and does not cause blocking, and without applying a surface treatment such as corona treatment, a coating layer on a substrate layer such as a cyclic olefin polymer, polycarbonate, or polyester. Is laminated with good adhesion, and an object is to provide a laminate having good flexibility and a method for producing the same.

（式（１）中、
Ｒ^ｃは、炭素原子数２〜１０の炭化水素基よりなる群から選ばれる４価の基；
Ｒ^ａは、炭素原子数２〜２０の炭化水素基よりなる群から選ばれる２＋ｎ価の基；
Ｑは、ＣＯＯＲｄ（Ｒｄは、水素原子、又は炭素原子数１〜１０の炭化水素基よりなる群から選ばれる１価の基）；
ｎは、置換基Ｑの置換数を示し、０≦ｎ≦２の実数；
Ｒ^ｂは、水素原子、又は炭素原子数１〜１０の炭化水素基よりなる群から選ばれる１価の基；
ｘ、ｙは、共重合モル比を示し、５／９５≦ｙ／ｘ≦９５／５を満たす実数
をそれぞれ示す。
Ｒ^ａ及びＲ^ｂは、それぞれ１種であってもよく、２種以上であってもよい。）
［３］ 前記アクリル系樹脂Ａが、メチルメタクリレート、ブチルメタクリレート、ヒドロキシエチルメタクリレートからなる群より選ばれるメタクリレート由来の構造単位と、メチルアクリレート、エチルアクリレート、ブチルアクリレート、ヒドロキシエチルアクリレートからなる群より選ばれるアクリレート由来の構造単位の少なくとも一方を含む、［１］又は［２］記載の積層体。
［４］ 前記アクリル系樹脂Ａの重量平均分子量が、１５０００〜５００００である、［１］〜［３］のいずれかに記載の積層体。
［５］ 前記アクリル系モノマーＢが、メタクリル酸及びアクリル酸からなる群より選ばれる一以上と多官能アルコールとの縮合物である、［１］〜［４］のいずれかに記載の積層体。
［６］ 前記アクリル系樹脂組成物の硬化物のＴｇは、前記基材層Ｙに含まれる前記樹脂のＴｇよりも低い、［１］〜［５］のいずれかに記載の積層体。
［７］ 環状オレフィン重合体、ポリカーボネート及びポリエステルからなる群より選ばれる一以上を含む基材層Ｘの少なくとも一方の面に、２０〜９０質量部のアクリル系樹脂Ａと、１０〜８０質量部のアクリル系モノマーＢと（但し、前記アクリル系樹脂Ａと前記アクリル系モノマーＢの合計を１００質量部とする）、重合開始剤とを含むアクリル系樹脂組成物を塗布して、前記アクリル系樹脂組成物の塗膜を形成する工程と、前記塗膜を、活性線により硬化又は熱硬化させて、Ｔｇが４０℃以上９０℃以下であるアクリル系樹脂組成物の硬化物からなる層Ｙを形成する工程と
を含む、積層体の製造方法。 [1] Substrate layer X containing a resin selected from the group consisting of a cyclic olefin polymer, polycarbonate and polyester, 20 to 90 parts by mass of acrylic resin A provided on at least one surface thereof, A layer Y composed of a cured product of an acrylic resin composition containing 80 parts by mass of an acrylic monomer B (provided that the total of the acrylic resin A and the acrylic monomer B is 100 parts by mass). The laminated body whose Tg of the hardened | cured material of the said acrylic resin composition is 40 degreeC or more and 90 degrees C or less.
[2] The base layer X is one or more cyclic groups selected from the group consisting of a cyclic olefin-α-olefin copolymer n1 represented by the formula (1) and a cyclic olefin ring-opening polymer n2. The laminate according to [1], including an olefin polymer.

(In the formula (1),
R ^c is a tetravalent group selected from the group consisting of hydrocarbon groups having 2 to 10 carbon atoms;
R ^a is a 2 + n-valent group selected from the group consisting of hydrocarbon groups having 2 to 20 carbon atoms;
Q is COORd (Rd is a monovalent group selected from the group consisting of a hydrogen atom or a hydrocarbon group having 1 to 10 carbon atoms);
n represents the number of substitutions of the substituent Q, and a real number of 0 ≦ n ≦ 2;
R ^b is a monovalent group selected from the group consisting of a hydrogen atom or a hydrocarbon group having 1 to 10 carbon atoms;
x and y represent copolymerization molar ratios and represent real numbers satisfying 5/95 ≦ y / x ≦ 95/5, respectively.
Each of R ^a and R ^b may be one type or two or more types. )
[3] The acrylic resin A is selected from a methacrylate-derived structural unit selected from the group consisting of methyl methacrylate, butyl methacrylate, and hydroxyethyl methacrylate, and a group consisting of methyl acrylate, ethyl acrylate, butyl acrylate, and hydroxyethyl acrylate. The laminate according to [1] or [2], comprising at least one of structural units derived from acrylate.
[4] The laminate according to any one of [1] to [3], wherein the acrylic resin A has a weight average molecular weight of 15,000 to 50,000.
[5] The laminate according to any one of [1] to [4], wherein the acrylic monomer B is a condensate of one or more selected from the group consisting of methacrylic acid and acrylic acid and a polyfunctional alcohol.
[6] The laminate according to any one of [1] to [5], wherein the cured product of the acrylic resin composition has a Tg lower than the Tg of the resin contained in the base material layer Y.
[7] 20 to 90 parts by mass of acrylic resin A and 10 to 80 parts by mass of at least one surface of the base material layer X including one or more selected from the group consisting of a cyclic olefin polymer, polycarbonate and polyester An acrylic resin composition containing an acrylic monomer B (however, the total of the acrylic resin A and the acrylic monomer B is 100 parts by mass) and a polymerization initiator is applied to the acrylic resin composition. A step of forming a coating film of the product, and the coating film is cured or thermally cured by active rays to form a layer Y made of a cured product of an acrylic resin composition having a Tg of 40 ° C. or more and 90 ° C. or less The manufacturing method of a laminated body including a process.

  According to the present invention, the coating layer is laminated with good adhesion on a substrate layer such as a cyclic olefin polymer, polycarbonate, or polyester without causing blocking and without performing surface treatment such as corona treatment, A laminate having good flexibility and a method for producing the same can be provided.

On at least one surface of the base material layer X, a layer Y made of a cured product of an acrylic resin composition containing the acrylic resin A and the acrylic monomer B in a predetermined ratio is provided.
That is, the layer Y made of a cured product of the acrylic resin composition is based on an acrylic resin composition that includes the acrylic monomer A and an acrylic monomer B that is reactive with actinic radiation, and a polymerization initiator. It can be obtained by coating at least one surface of the layer X and curing it with ultraviolet rays or the like. Since the acrylic resin composition contains the acrylic resin A and the acrylic monomer B that is reactive to the active ray, in addition to the high adhesion that the acrylic resin A itself has, the acrylic monomer B contains The diffusion effect (or anchor effect) to the base material layer X can be imparted. And by adjusting the content ratio of the acrylic resin A and the acrylic monomer B to a predetermined range, the flexibility and adhesion of the acrylic resin A itself and the adhesion imparted by the acrylic monomer B are Good balance can be achieved. Thereby, it is possible to obtain good adhesion with the base material layer X and good flexibility and flexibility without performing surface treatment that improves the surface wettability of the corona treatment or the primer layer.

  Furthermore, by adjusting the Tg of the layer Y made of a cured product of the acrylic resin composition to 40 ° C. or more and 90 ° C. or less, the base layer X is given further flexibility and flexibility without blocking. can do.

  Thus, by adjusting the composition and thermophysical property of the layer Y made of a cured product of the acrylic resin composition as appropriate, it has good adhesion to the base material layer X without performing surface treatment such as corona treatment, Since flexibility can be imparted, the flexibility of the base material layer X can be improved. The present invention has been made based on such findings.

1. Laminated body The laminated body of this invention contains the base material layer X and the layer Y which consists of the hardened | cured material of the acrylic resin composition provided in the at least one surface.

1-1. Base material layer X
The base material layer X preferably contains one or more resins selected from the group consisting of a cyclic olefin polymer, a polycarbonate, and a polyester, and since the transparency and heat resistance are particularly excellent, the base layer X may contain a cyclic olefin polymer. More preferred.

  The cyclic olefin polymer may be a cyclic olefin addition polymer n1 or a cyclic olefin ring-opening polymer n2.

（式（１）中、
Ｒ^ｃは、炭素原子数２〜１０の炭化水素基よりなる群から選ばれる４価の基；
Ｒ^ａは、炭素原子数２〜２０の炭化水素基よりなる群から選ばれる２＋ｎ価の基；
Ｑは、ＣＯＯＲｄ（Ｒｄは、水素原子、又は炭素原子数１〜１０の炭化水素基よりなる群から選ばれる１価の基）；
ｎは、置換基Ｑの置換数を示し、０≦ｎ≦２の実数；
Ｒ^ｂは、水素原子、又は炭素原子数１〜１０の炭化水素基よりなる群から選ばれる１価の基；
ｘ、ｙは、共重合モル比を示し、５／９５≦ｙ／ｘ≦９５／５を満たす実数
をそれぞれ示す。
Ｒ^ａ及びＲ^ｂは、それぞれ１種であってもよく、２種以上を任意の割合で有していてもよい。） (Cyclic olefin addition polymer n1)
The cyclic olefin addition polymer n1 is preferably a copolymer n1 of a cyclic olefin and an α olefin represented by the formula (1).

(In the formula (1),
R ^c is a tetravalent group selected from the group consisting of hydrocarbon groups having 2 to 10 carbon atoms;
R ^a is a 2 + n-valent group selected from the group consisting of hydrocarbon groups having 2 to 20 carbon atoms;
Q is COORd (Rd is a monovalent group selected from the group consisting of a hydrogen atom or a hydrocarbon group having 1 to 10 carbon atoms);
n represents the number of substitutions of the substituent Q, and a real number of 0 ≦ n ≦ 2;
R ^b is a monovalent group selected from the group consisting of a hydrogen atom or a hydrocarbon group having 1 to 10 carbon atoms;
x and y represent copolymerization molar ratios and represent real numbers satisfying 5/95 ≦ y / x ≦ 95/5, respectively.
Each of R ^a and R ^b may be one type, or may have two or more types in any proportion. )

R ^a may further form a ring structure. Preferred examples of the ring structure include norbornene and tetracyclododecene. The ring structure may further have a substituent such as an alkyl group. The ring composed of R ^a and R ^c corresponds to an adduct of a cyclic olefin described later.

R ^b is preferably a hydrogen atom, a methyl group or an ethyl group, and particularly preferably a hydrogen atom.

  x and y are preferably 50/50 ≦ y / x ≦ 95/5, and more preferably 55/45 ≦ y / x ≦ 80/20.

  The copolymer n1 of the cyclic olefin and the α-olefin represented by the formula (1) is preferably a copolymer composed of a cyclic olefin and ethylene.

  Cyclic olefins include bicyclo [2.2.1] hept-2-ene (common name: norbornene), tetracyclo [4.4.0.12, 5.17,10] -3-dodecene (common name: tetracyclo). Dodecene), 1,4-methano-1,4,4a, 9a-tetrahydrofluorene, cyclopentadiene-benzyne adduct, and cyclopentadiene-acenaphthylene adduct are preferably used. , Bicyclo [2.2.1] -2-heptene and tetracyclo [4.4.0.12,5.17,10] -3-dodecene are more preferable.

  The copolymer n1 of a cyclic olefin and an α-olefin represented by the formula (1) may be a copolymer of a cyclic olefin and an α-olefin having 4 to 12 carbon atoms.

  As the cyclic olefin, those similar to those described above can be used, and examples include norbornene and substituted norbornene, and norbornene is preferable. A cyclic olefin can be used individually by 1 type or in combination of 2 or more types.

  Examples of the α-olefin having 4 to 12 carbon atoms include 1-butene, 1-hexene, 4-methyl 1-pentene, 1-octene, 1-decene and the like.

  Examples of the copolymer of a cyclic olefin and an α-olefin having 4 to 12 carbon atoms include the polymers described in paragraphs 0056 to 0070 of International Publication No. 2015/178145.

(Ring-opening polymer n2 of cyclic olefin)
Examples of the ring-opening polymer n2 of the cyclic olefin include, for example, a ring-opening polymer of a norbornene-based monomer, and a ring-opening copolymer of a norbornene-based monomer and another monomer capable of ring-opening copolymerization therewith Or a hydride thereof.

  Examples of the norbornene-based monomer include bicyclo [2.2.1] hept-2-ene (common name: norbornene) and its derivatives (having a substituent in the ring), tricyclo [4.3.01, 6.12,5] deca-3,7-diene (common name dicyclopentadiene) and derivatives thereof, 7,8-benzotricyclo [4.3.0.12,5] dec-3-ene (common name) Methanotetrahydrofluorene: 1,4-methano-1,4,4a, 9a-tetrahydrofluorene) and derivatives thereof, tetracyclo [4.4.0.12,5.17,10] -3-dodecene (common name) : Tetracyclododecene) and derivatives thereof.

Examples of the substituent substituted on the ring of these derivatives include an alkyl group, an alkylene group, a vinyl group, an alkoxycarbonyl group, and an alkylidene group. In addition, a substituent can have 1 piece or 2 or more pieces.
Examples of such derivatives having a substituent in the ring include 8-methoxycarbonyl-tetracyclo [4.4.0.12,5.17,10] dodec-3-ene, 8-methyl-8-methoxycarbonyl. -Tetracyclo [4.4.0.12,5.17,10] dodec-3-ene, 8-ethylidene-tetracyclo [4.4.0.12,5.17,10] dodec-3-ene, etc. Can be mentioned.

  These norbornene monomers are used alone or in combination of two or more.

  Examples of other monomers capable of ring-opening copolymerization with norbornene monomers include monocyclic cyclic olefin monomers such as cyclohexene, cycloheptene, and cyclooctene.

  A ring-opening polymer of a norbornene-based monomer, or a ring-opening copolymer of a norbornene-based monomer and another monomer capable of ring-opening copolymerization with a monomer component is a known ring-opening polymer. It can be obtained by polymerization in the presence of a polymerization catalyst.

  As the ring-opening polymerization catalyst, for example, a catalyst comprising a metal halide such as ruthenium or osmium, a nitrate or acetylacetone compound, and a reducing agent; a metal halide or acetylacetone compound such as titanium, zirconium, tungsten or molybdenum; A catalyst comprising an organoaluminum compound can be used.

  A hydride of a ring-opening polymer of a norbornene-based monomer or a hydride of a ring-opening polymer of a norbornene-based monomer and another monomer capable of ring-opening copolymerization is usually the above-mentioned ring-opening polymer. It can be obtained by adding a known hydrogenation catalyst containing a transition metal such as nickel or palladium to the polymer solution and hydrogenating the carbon-carbon unsaturated bond.

  A cyclic olefin polymer may be used individually by 1 type, and may use 2 or more types together.

(Physical properties of base material layer X)
The thickness of the base material layer X is preferably 10 to 300 μm. When the thickness of the base material layer X is 25 μm or more, the laminate is likely to have sufficient mechanical strength. When the thickness of the base material layer X is 250 μm or less, the flexibility of the laminate is difficult to be impaired. As for the thickness of the base material layer X, it is more preferable that it is 25-250 micrometers.

  The Tg of the base material layer X can be, for example, 100 to 200 ° C. When the Tg of the base material layer X is 120 ° C. or higher, good heat resistance is easily obtained. The Tg of the base material layer X can be measured by a DSC method. The measurement conditions are the same as in the examples described later.

1-2. Layer Y made of a cured product of an acrylic resin composition
The layer Y made of a cured product of the acrylic resin composition is a layer obtained by curing an acrylic resin composition containing the acrylic resin A, the acrylic monomer B, and a polymerization initiator. That is, the layer Y made of the cured product of the acrylic resin composition includes the acrylic resin A and the cured product of the acrylic monomer B.

(Acrylic resin A)
Acrylic resin A is a methacrylate-derived structural unit selected from the group consisting of methyl methacrylate, butyl methacrylate, and hydroxyethyl methacrylate, and an acrylate-derived structure selected from the group consisting of methyl acrylate, ethyl acrylate, butyl acrylate, and hydroxyethyl acrylate. It is preferable to include at least one of the units.

  Among them, the acrylic resin A is preferably a copolymer including a structural unit derived from methacrylate and a structural unit derived from acrylate, and is a copolymer including a structural unit derived from methyl methacrylate and a structural unit derived from butyl acrylate. More preferably, it is a polymer.

  The acrylic resin A preferably has a weight average molecular weight Mw of about 15,000 to 50,000. If the weight average molecular weight Mw of the acrylic resin A is 15000 or more, the cohesion of the polymer molecules is increased, so that adhesion is easily imparted, and if it is 50000 or less, the coating property of the acrylic resin composition is hardly impaired. In addition, it is easy to impart sufficient flexibility to the laminate. The weight average molecular weight Mw of the acrylic resin A is more preferably 20,000 to 40,000. The weight average molecular weight of the acrylic resin A can be measured, for example, in terms of PMMA by gel permeation chromatography (GPC).

(Acrylic monomer B)
The acrylic monomer B is preferably a compound having one or more acryloyl groups or methacryloyl groups in the molecule.

  As the compound having one acryloyl group or methacryloyl group in the molecule, at least one selected from the group consisting of methyl methacrylate, methyl acrylate, ethyl acrylate, butyl acrylate, butyl methacrylate, hydroxyethyl acrylate, and hydroxyethyl methacrylate is used. be able to. Depending on the type of the base material layer X, a penetration / diffusion effect due to a compound having one acryloyl group or methacryloyl group in the molecule may be expected. In that case, methyl methacrylate and methyl acrylate are particularly preferable.

  As a compound having 2 to 6 acryloyl groups or methacryloyl groups in the molecule, a condensate of at least one selected from the group consisting of methacrylic acid and acrylic acid and a polyfunctional alcohol can be used.

As polyfunctional alcohol, it is preferable that it is 2-6 functional alcohol, and can mention the following.
Bifunctional: ethylene glycol, diethylene glycol, propylene glycol, butylene glycol, hexamethylene glycol, neopentyl glycol Trifunctional: glycerin, trimethylolpropane Tetrafunctional: ditrimethylolpropane Hexafunctional: pentaerythritol, pentaerythritol

Examples of condensates of polyfunctional alcohols with at least one selected from the group consisting of methacrylic acid and acrylic acid include the following compounds.
Hexamethylene glycol diacrylate, trimethylolpropane triacrylate, ditrimethylolpropane tetraacrylate, pentaerythritol tetraacrylate, dipentaerythritol hexaacrylate

  Further, acrylate or methacrylate having a urethane bond or an ether bond in the molecular skeleton can also be used as appropriate.

  Among these, the acrylic monomer B contains a compound having 2 to 6 acryloyl groups or methacryloyl groups in the molecule because the effect of imparting a crosslinked structure to the coating film is expected. preferable. The compound having 2 to 6 acryloyl groups or methacryloyl groups in the molecule is preferably a condensate of a polyfunctional alcohol with at least one selected from the group consisting of methacrylic acid and acrylic acid, and forms a crosslinked structure. And a condensate of at least one selected from the group consisting of methacrylic acid and acrylic acid and a tri- to 6-functional alcohol from the point that the adhesion with the base material layer X can be made stronger. preferable.

  Content ratio A / B of acrylic resin A and acrylic monomer B in acrylic resin composition (cured product of acrylic resin A and acrylic monomer B in layer Y consisting of a cured product of acrylic resin composition) Content ratio) is 20-90 parts by mass / 10-80 parts by mass, preferably 20-90 parts by mass / 80-10 parts by mass, and 30-80 parts by mass / 70-20 parts by mass. It is more preferable, and it is still more preferable that it is 40-70 mass parts / 60-30 mass parts. When the content ratio of the acrylic resin A is increased, flexibility and adhesion are easily imparted to the base material layer X. When the content ratio of the acrylic monomer B is increased, an effect of improving the film strength due to the crosslinked structure is obtained. The effect of improving adhesion due to the diffusion effect (or anchor effect) on the layer X can also be expected. However, the total of acrylic resin A and acrylic monomer B is 100 parts by mass.

  When the acrylic resin composition contains, as the acrylic monomer B, a condensate of one or more selected from the group consisting of methacrylic acid and acrylic acid and a polyfunctional alcohol, the layer Y made of a cured product of the acrylic resin composition The content ratio of the cured product of the acrylic resin A and the acrylic monomer B in can be confirmed by measuring the content ratio of the polyfunctional alcohol moiety by GC-MS.

(Physical properties of cured product of acrylic resin composition)
The glass transition temperature (Tg) of the cured product of the acrylic resin composition is preferably lower than the Tg of the resin contained in the base material layer X from the viewpoint of imparting sufficient flexibility to the laminate. Specifically, the Tg of the cured product of the acrylic resin composition is preferably 40 ° C. or higher and 90 ° C. or lower, and more preferably 50 ° C. to 80 ° C. When the Tg of the cured product of the acrylic resin composition is 40 ° C. or higher, blocking (stickiness) is less likely to occur, and when it is 90 ° C. or lower, flexibility and flexibility are not easily impaired.

  The Tg of the cured product of the acrylic resin composition can be measured by a DSC method after peeling the layer Y made of the cured product of the acrylic resin composition from the base material layer X. The measurement conditions are as in the examples described later.

  The Tg of the cured product of the acrylic resin composition depends on the content ratio A / B of the acrylic resin A and the acrylic monomer B in the acrylic resin composition, the Tg of the acrylic resin A, the Tg of the acrylic monomer B, etc. Can be adjusted.

  The Tg of the acrylic resin A can be adjusted by, for example, the content ratio of the structural unit derived from methacrylate and the structural unit derived from acrylate. In a copolymer including a structural unit derived from methyl methacrylate and a structural unit derived from butyl acrylate, Tg can be increased by increasing the content ratio of the structural unit derived from methyl methacrylate.

  The Tg of the acrylic monomer B can be adjusted by the composition of the acrylic monomer B, for example. Tg increases as the number of functional groups of the acrylic monomer B, that is, the number of acryloyl groups or methacryloyl groups in the molecule increases. For example, in the system containing hexamethylene glycol diacrylate and dipentaerythritol hexaacrylate as the acrylic monomer B, Tg can be increased by increasing the content ratio of dipentaerythritol hexaacrylate.

1-3. Common Items In order to increase the flexibility of the laminate of the present invention, it is preferable that the relative thickness of the layer Y made of a cured product of the acrylic resin composition with respect to the base material layer X is a certain level or more. Specifically, the thickness ratio (X / Y) of the base material layer X and the layer Y made of a cured product of the acrylic resin composition is preferably 10 to 300 μm / 1 to 20 μm, and preferably 25 to 250 μm. More preferably, it is / 2 to 10 μm. When there are a plurality of layers Y, the thickness of the layer Y made of a cured product of the acrylic resin composition means the total thickness thereof.

  As described above, the layer Y made of a cured product of the acrylic resin composition may be provided on one surface of the base material layer X, or may be provided on both surfaces. The layer Y made of a cured product of the acrylic resin composition is preferably provided on both surfaces of the base material layer X in terms of easily imparting sufficient flexibility to the laminate. The layers Y made of a cured product of the acrylic resin composition provided on both surfaces of the base material layer X may have the same thickness or different thicknesses, and suppress warpage and the like. Then, it is preferable that it is the same thickness.

2. Method for Producing Laminate The laminate of the present invention comprises a step of applying the acrylic resin composition described above to at least one surface of the base material layer X to form a coating film of the acrylic resin composition, The coating film can be cured or thermally cured with actinic radiation to form a layer Y made of a cured product of an acrylic resin composition having a Tg of 40 ° C. or higher and 90 ° C. or lower.

  The acrylic resin composition includes the aforementioned acrylic resin A, the aforementioned acrylic monomer B, and a polymerization initiator.

The polymerization initiator can be a photopolymerization initiator or a thermal polymerization initiator. The photopolymerization initiator is a radical photopolymerization initiator, and examples thereof include alkylphenone compounds, acylphosphine oxide compounds, titanocene compounds, and oxime ester compounds.
Examples of alkylphenone compounds include benzyl dimethyl ketals such as 2,2-dimethoxy-1,2-diphenylethane-1-one (IRGACURE 651); 2-methyl-2-morpholino (4-thiomethylphenyl) propane Α-aminoalkylphenones such as -1-one (IRGACURE 907); α-hydroxyalkylphenones such as 1-hydroxy-cyclohexyl-phenyl-ketone (IRGACURE 184) and the like are included. Examples of the acyl phosphine oxide compound include 2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide. The titanocene-based compound includes bis (η5-2,4-cyclopentadien-1-yl) -bis (2,6-difluoro-3- (1H-pyrrol-1-yl) -phenyl) titanium and the like. Examples of the oxime ester compound include 1,2-octanedione-1- [4- (phenylthio) -2- (O-benzoyloxime)] (IRGACURE OXE 01) and the like.

  The thermal polymerization initiator is a thermal radical polymerization initiator, and examples thereof include organic peroxide compounds and azo compounds. Examples of organic peroxide compounds include ketone peroxide compounds such as methyl ethyl ketone peroxide; peroxyketal compounds such as 1,1-di (t-butyloxy) cyclohexane; t-butyl peroxybivalate, etc. Alkyl peroxyester compounds; diacyl peroxide compounds such as dilauroyl peroxide; peroxydicarbonate compounds such as (2-ethylhexyl) peroxydicarbonate; peroxycarbonates such as t-butylperoxyisopropyl carbonate Compounds; Dialkyl peroxide compounds such as di-t-butyl peroxide; hydroperoxide compounds such as t-amyl hydroperoxide and the like. Specific examples of the azo compound include 1,1′-azobis (2,4-cyclohexane) -1-carbonitrile, 2,2′-azobis [(2-imidazoline-2-el) propane] disulfate dihydride. Water-soluble azo compounds such as late; oil-soluble azo compounds such as 1-[(cyano-1-methyl) azo] formamide; polymer azo compounds and the like.

  The content of the polymerization initiator is preferably 0.5 to 10% by mass with respect to the total mass of the acrylic monomer B.

  The acrylic resin composition may further contain a solvent according to the coating method described later. Viscosity, solid content, etc. can be adjusted by further diluting the acrylic resin composition with a solvent or the like.

  The application of the acrylic resin composition can be generally performed by a known printing method or coating method. Examples of the printing method include gravure printing and screen printing, and examples of the coating method include gravure, die coating, roll coating, and the like, which can be appropriately selected according to a desired appearance and film thickness.

  Ultraviolet rays or visible light can be used as the actinic radiation that irradiates the coating film of the acrylic resin composition.

  In the prior art, a base material layer, particularly a base material layer made of a cyclic olefin polymer, had to be modified by corona discharge or plasma treatment on the surface layer of the cyclic olefin polymer in order to improve adhesion to an acrylic resin. However, according to the acrylic resin composition of the present invention, a laminate can be obtained without performing such surface treatment.

3. Applications The laminate of the present invention can be used for various display devices, for example. For example, the laminate of the present invention can be used as a backlight member for a liquid crystal display device or a protective film for a polarizing plate. Moreover, it can be used as a barrier film for an organic EL display device by forming a metal oxide or the like on the laminate, and in a flexible organic EL display device, the element is used due to its barrier property and thermal dimensional stability. It can be used as a substrate or a transparent substrate. According to the present invention, a laminate can be obtained without performing a surface treatment such as corona on the base material layer, so that it is possible to suppress changes in the surface state over time, and it is more suitable for optical applications by reducing foreign matters due to static electricity. Become.

  In the following, the invention will be described in more detail with reference to examples. These examples do not limit the scope of the present invention.

1. Material of laminate 1) Base material layer X
Cyclic olefin film made of a copolymer of ethylene and tetracyclododecene (Tg by DSC method: 150 ° C.), thickness 50 μm

2) Material of acrylic resin composition (acrylic resin A)
As acrylic resin A, the copolymer of the following component 1 and 2 was used. The weight average molecular weight of the acrylic resin A was between 20,000 and 30,000, respectively.
Component 1: Methyl methacrylate Component 2: Butyl acrylate (acrylic monomer B)
Hexamethylene glycol diacrylate Dipentaerythritol hexaacrylate (photoinitiator)
IRGACURE 184 manufactured by BASF (1-hydroxy-cyclohexyl-phenyl-ketone)

2. Production and evaluation of laminate (production of laminates 1-1 to 1-6)
1) Preparation of acrylic resin composition After fixing the content ratio A / B of acrylic resin A and acrylic monomer B in the acrylic resin composition at 10/90, the Tg of the cured product is shown in Table 1. By adjusting at least one of the type of acrylic resin A (copolymerization ratio of the copolymer of constituent components 1 and 2) and the composition of acrylic monomer B (component ratio) so that the value becomes A composition was obtained.

2) Production of Laminate The above prepared acrylic resin composition is cured on both sides of a 50 μm-thick cyclic olefin film (copolymer film of ethylene and tetracyclododecene) that is the base material layer X. Each was applied to 3 μm and then dried. This was further irradiated with ultraviolet rays at a light amount of 300 mJ and cured to form a layer Y made of a cured product of the acrylic resin composition, and laminates 1-1 to 1-6 were obtained.

(Production of laminates 2-1 to 2-6)
After fixing the content ratio A / B of the acrylic resin A and the acrylic monomer B in the acrylic resin composition at 20/80, the acrylic resin so that the Tg of the cured product becomes the value shown in Table 1. Laminate 2- is the same as Laminate 1-1 except that at least one of the type of A (copolymerization ratio of copolymers of constituent components 1 and 2) and the composition (component ratio) of acrylic monomer B is adjusted. 1-2-6 were obtained.

(Preparation of laminates 3-1 to 3-6)
After fixing the content ratio A / B of the acrylic resin A and the acrylic monomer B in the acrylic resin composition at 50/50, the acrylic resin so that the Tg of the cured product becomes the value shown in Table 2. Laminate 3- is the same as Laminate 1-1 except that at least one of the type of A (copolymerization ratio of copolymers of constituent components 1 and 2) and the composition (component ratio) of acrylic monomer B is adjusted. 1-3-6 were obtained.

(Preparation of laminates 4-1 to 4-6)
After fixing the content ratio A / B of the acrylic resin A and acrylic monomer B in the acrylic resin composition at 90/10, the acrylic resin so that the Tg of the cured product becomes the value shown in Table 2. Laminate 4- is the same as Laminate 1-1 except that at least one of the type of A (copolymerization ratio of copolymer of constituent components 1 and 2) and the composition (component ratio) of acrylic monomer B is adjusted. 1-4-6 were obtained.

(Production of laminates 5-1 to 5-6)
After fixing the content ratio A / B of the acrylic resin A and the acrylic monomer B in the acrylic resin composition at 95/5, the acrylic resin so that the Tg of the cured product becomes the value shown in Table 3 Laminate 5- is the same as Laminate 1-1 except that at least one of the type of A (copolymerization ratio of copolymers of constituents 1 and 2) and the composition (component ratio) of acrylic monomer B is adjusted. 1-5-6 were obtained.

  The Tg of the cured product of the acrylic resin composition used for the production of each laminate, and the flexibility, adhesion, and blocking of the obtained laminate were evaluated by the following methods.

<Tg of cured product>
The acrylic resin composition used for the production of each laminate was coated on a polypropylene sheet and then photocured under the same conditions as described above to form a cured film of the acrylic resin composition. The obtained cured film was peeled from the polypropylene sheet, and its Tg was measured by DSC method using a DSC60A manufactured by Shimadzu Corporation at a heating rate of 20 ° C./min.

<Flexibility>
For each of the base material before application of the acrylic resin composition (uncoated base material) and the obtained laminate, the number of bendings until breaking was measured according to JIS P 8115 using a MIT tester. did. The measurement was performed under the following conditions.
(Test conditions)
Load: 0.5kgf
Bending angle: 270 °
Bending speed: 127 times / min. Evaluation was made based on the following criteria by visual judgment.
○: Endures at the number of folding times greater than or equal to the uncoated substrate ×: Cracks occur at the number of folding times less than or equal to the uncoated substrate

<Adhesion>
The adhesion between the base material layer X of the obtained laminate and the layer Y made of a cured product of the acrylic resin composition was evaluated by a cross-cut test according to JIS K5600-5-6. The total number of grids was 25, and the number of eyes remaining after peeling was counted and evaluated according to the following criteria.
○: No peeling ×: There is peeling at one or more locations

<Blocking>
The presence or absence of tack (stickiness) on the surface of the obtained laminate was judged by touch.
○: Without tack (stickiness) ×: With tack (stickiness)

  The evaluation results of the laminates 1-1 to 1-6 and 2-1 to 2-6 are shown in Table 1, and the evaluation results of the laminates 3-1 to 3-6 and 4-1 to 4-6 are shown in Table 2. Table 3 shows the evaluation results of the laminates 5-1 to 5-6. “-” In the table indicates that the measurement has not been performed.

  As shown in Tables 1 to 3, the content ratio A / B of the acrylic resin A and the acrylic monomer B in the acrylic resin composition is in the range of 20/80 to 90/10, and the Tg of the cured product Of the laminates (laminates 2-2 to 2-5, 3-2 to 3-5, 4-2 to 4-5) in which the temperature is in the range of 40 to 90 ° C. It can be seen that both the adhesiveness and the flexibility are high.

  On the other hand, even if the Tg of the cured product is within the above range, the laminates 1-1 to 1-6 and 5-1 to which the content ratio A / B of the acrylic resin A and the acrylic monomer B is outside the above range. It can be seen that 5-6 has low adhesion and flexibility with the base material layer X. Specifically, since the laminates 1-1 to 1-6 have an excessive content ratio of the acrylic monomer B, the layer Y made of a cured product is hard, and sufficient adhesion and flexibility cannot be obtained. Conceivable. It is considered that the laminates 5-1 to 5-6 were unable to obtain flexibility and adhesion because the content ratio of the acrylic monomer B was too small. Further, even when the content ratio A / B is within the above range, the laminates 2-6, 3-6, and 4-6 in which the Tg of the cured product exceeds 90 ° C. are all low in flexibility and flexible / It can be seen that the adhesion is low.

  According to the present invention, without causing blocking, the coating layer can be laminated with good adhesion without performing surface treatment such as corona treatment on a substrate layer such as a cyclic olefin polymer, polycarbonate or polyester, A laminate having flexibility and a method for manufacturing the same can be provided.

Claims (7)

A base material layer X containing a resin selected from the group consisting of a cyclic olefin polymer, polycarbonate and polyester;
20 to 90 parts by mass of acrylic resin A and 10 to 80 parts by mass of acrylic monomer B (provided that the total of acrylic resin A and acrylic monomer B is provided on at least one surface) Layer Y made of a cured product of an acrylic resin composition containing 100 parts by mass),
Including
The laminated body whose Tg of the hardened | cured material of the said acrylic resin composition is 40 to 90 degreeC. The base material layer X is one or more cyclic olefin polymers selected from the group consisting of a cyclic olefin-α-olefin copolymer n1 represented by the formula (1) and a cyclic olefin ring-opening polymer n2. The laminated body of Claim 1 containing this.

(In the formula (1),
R ^c is a tetravalent group selected from the group consisting of hydrocarbon groups having 2 to 10 carbon atoms;
R ^a is a 2 + n-valent group selected from the group consisting of hydrocarbon groups having 2 to 20 carbon atoms;
Q is COORd (Rd is a monovalent group selected from the group consisting of a hydrogen atom or a hydrocarbon group having 1 to 10 carbon atoms);
n represents the number of substitutions of the substituent Q, and a real number of 0 ≦ n ≦ 2;
R ^b is a monovalent group selected from the group consisting of a hydrogen atom or a hydrocarbon group having 1 to 10 carbon atoms;
x and y represent copolymerization molar ratios and represent real numbers satisfying 5/95 ≦ y / x ≦ 95/5, respectively.
Each of R ^a and R ^b may be one type or two or more types. )   The acrylic resin A is derived from a methacrylate-derived structural unit selected from the group consisting of methyl methacrylate, butyl methacrylate, and hydroxyethyl methacrylate, and from an acrylate selected from the group consisting of methyl acrylate, ethyl acrylate, butyl acrylate, and hydroxyethyl acrylate. The laminated body of Claim 1 or 2 containing at least one of a structural unit.   The laminated body as described in any one of Claims 1-3 whose weight average molecular weights of the said acrylic resin A are 15000-50000.   The laminate according to any one of claims 1 to 4, wherein the acrylic monomer B is a condensate of one or more selected from the group consisting of methacrylic acid and acrylic acid and a polyfunctional alcohol.   The laminate according to any one of claims 1 to 5, wherein Tg of the cured product of the acrylic resin composition is lower than Tg of the resin contained in the base material layer Y. On at least one surface of the base material layer X containing at least one selected from the group consisting of a cyclic olefin polymer, polycarbonate and polyester, 20 to 90 parts by mass of acrylic resin A and 10 to 80 parts by mass of acrylic monomer B. (However, the acrylic resin A and the acrylic monomer B are 100 parts by mass in total) and an acrylic resin composition containing a polymerization initiator are applied, and the acrylic resin composition is applied. Forming a film;
A method of producing a laminate, comprising: curing or thermally curing the coating film with active rays to form a layer Y made of a cured product of an acrylic resin composition having a Tg of 40 ° C. or higher and 90 ° C. or lower. .