JP2019131682A - Curable polymer composition and laminate - Google Patents
Curable polymer composition and laminate Download PDFInfo
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- JP2019131682A JP2019131682A JP2018014230A JP2018014230A JP2019131682A JP 2019131682 A JP2019131682 A JP 2019131682A JP 2018014230 A JP2018014230 A JP 2018014230A JP 2018014230 A JP2018014230 A JP 2018014230A JP 2019131682 A JP2019131682 A JP 2019131682A
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- polymer
- meth
- acrylate
- polymer composition
- curable polymer
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- 229920000642 polymer Polymers 0.000 title claims abstract description 178
- 239000000203 mixture Substances 0.000 title claims abstract description 75
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 claims abstract description 97
- 239000011248 coating agent Substances 0.000 claims description 34
- 238000000576 coating method Methods 0.000 claims description 34
- 239000002904 solvent Substances 0.000 claims description 32
- 239000003960 organic solvent Substances 0.000 claims description 9
- 230000008859 change Effects 0.000 claims description 6
- -1 2-hydroxypropyl Chemical group 0.000 description 18
- 238000000034 method Methods 0.000 description 18
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 16
- 239000000178 monomer Substances 0.000 description 12
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 12
- ARXJGSRGQADJSQ-UHFFFAOYSA-N 1-methoxypropan-2-ol Chemical compound COCC(C)O ARXJGSRGQADJSQ-UHFFFAOYSA-N 0.000 description 11
- 239000003795 chemical substances by application Substances 0.000 description 11
- 239000010954 inorganic particle Substances 0.000 description 11
- 239000011347 resin Substances 0.000 description 11
- 229920005989 resin Polymers 0.000 description 11
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 10
- 230000009477 glass transition Effects 0.000 description 10
- 239000000047 product Substances 0.000 description 10
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 9
- 239000007787 solid Substances 0.000 description 9
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 8
- 238000001723 curing Methods 0.000 description 8
- 238000006116 polymerization reaction Methods 0.000 description 8
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 7
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 7
- 125000003647 acryloyl group Chemical group O=C([*])C([H])=C([H])[H] 0.000 description 7
- 239000008367 deionised water Substances 0.000 description 7
- 229910021641 deionized water Inorganic materials 0.000 description 7
- 238000004519 manufacturing process Methods 0.000 description 7
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 7
- 229910052753 mercury Inorganic materials 0.000 description 7
- 239000000243 solution Substances 0.000 description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 7
- WYGWHHGCAGTUCH-UHFFFAOYSA-N 2-[(2-cyano-4-methylpentan-2-yl)diazenyl]-2,4-dimethylpentanenitrile Chemical compound CC(C)CC(C)(C#N)N=NC(C)(C#N)CC(C)C WYGWHHGCAGTUCH-UHFFFAOYSA-N 0.000 description 6
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 6
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 6
- 239000007900 aqueous suspension Substances 0.000 description 6
- 238000006243 chemical reaction Methods 0.000 description 6
- 238000011156 evaluation Methods 0.000 description 6
- RIOQSEWOXXDEQQ-UHFFFAOYSA-N triphenylphosphine Chemical compound C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 RIOQSEWOXXDEQQ-UHFFFAOYSA-N 0.000 description 6
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 5
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- 230000015572 biosynthetic process Effects 0.000 description 5
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- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 4
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- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 4
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- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 3
- TXBCBTDQIULDIA-UHFFFAOYSA-N 2-[[3-hydroxy-2,2-bis(hydroxymethyl)propoxy]methyl]-2-(hydroxymethyl)propane-1,3-diol Chemical compound OCC(CO)(CO)COCC(CO)(CO)CO TXBCBTDQIULDIA-UHFFFAOYSA-N 0.000 description 3
- 125000000954 2-hydroxyethyl group Chemical group [H]C([*])([H])C([H])([H])O[H] 0.000 description 3
- JIGUQPWFLRLWPJ-UHFFFAOYSA-N Ethyl acrylate Chemical compound CCOC(=O)C=C JIGUQPWFLRLWPJ-UHFFFAOYSA-N 0.000 description 3
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- 239000007864 aqueous solution Substances 0.000 description 3
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 3
- SWXVUIWOUIDPGS-UHFFFAOYSA-N diacetone alcohol Chemical compound CC(=O)CC(C)(C)O SWXVUIWOUIDPGS-UHFFFAOYSA-N 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 3
- 125000003055 glycidyl group Chemical group C(C1CO1)* 0.000 description 3
- VOZRXNHHFUQHIL-UHFFFAOYSA-N glycidyl methacrylate Chemical compound CC(=C)C(=O)OCC1CO1 VOZRXNHHFUQHIL-UHFFFAOYSA-N 0.000 description 3
- 239000003999 initiator Substances 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 238000000465 moulding Methods 0.000 description 3
- NWVVVBRKAWDGAB-UHFFFAOYSA-N p-methoxyphenol Chemical compound COC1=CC=C(O)C=C1 NWVVVBRKAWDGAB-UHFFFAOYSA-N 0.000 description 3
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 description 3
- PNJWIWWMYCMZRO-UHFFFAOYSA-N pent‐4‐en‐2‐one Natural products CC(=O)CC=C PNJWIWWMYCMZRO-UHFFFAOYSA-N 0.000 description 3
- 239000003505 polymerization initiator Substances 0.000 description 3
- 238000010992 reflux Methods 0.000 description 3
- KBPLFHHGFOOTCA-UHFFFAOYSA-N 1-Octanol Chemical compound CCCCCCCCO KBPLFHHGFOOTCA-UHFFFAOYSA-N 0.000 description 2
- BBMCTIGTTCKYKF-UHFFFAOYSA-N 1-heptanol Chemical compound CCCCCCCO BBMCTIGTTCKYKF-UHFFFAOYSA-N 0.000 description 2
- XLPJNCYCZORXHG-UHFFFAOYSA-N 1-morpholin-4-ylprop-2-en-1-one Chemical compound C=CC(=O)N1CCOCC1 XLPJNCYCZORXHG-UHFFFAOYSA-N 0.000 description 2
- AVTLBBWTUPQRAY-UHFFFAOYSA-N 2-(2-cyanobutan-2-yldiazenyl)-2-methylbutanenitrile Chemical compound CCC(C)(C#N)N=NC(C)(CC)C#N AVTLBBWTUPQRAY-UHFFFAOYSA-N 0.000 description 2
- PTTPXKJBFFKCEK-UHFFFAOYSA-N 2-Methyl-4-heptanone Chemical compound CC(C)CC(=O)CC(C)C PTTPXKJBFFKCEK-UHFFFAOYSA-N 0.000 description 2
- LPEKGGXMPWTOCB-UHFFFAOYSA-N 8beta-(2,3-epoxy-2-methylbutyryloxy)-14-acetoxytithifolin Natural products COC(=O)C(C)O LPEKGGXMPWTOCB-UHFFFAOYSA-N 0.000 description 2
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- 229920002799 BoPET Polymers 0.000 description 2
- DKPFZGUDAPQIHT-UHFFFAOYSA-N Butyl acetate Natural products CCCCOC(C)=O DKPFZGUDAPQIHT-UHFFFAOYSA-N 0.000 description 2
- MRABAEUHTLLEML-UHFFFAOYSA-N Butyl lactate Chemical compound CCCCOC(=O)C(C)O MRABAEUHTLLEML-UHFFFAOYSA-N 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 description 2
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 2
- AEMRFAOFKBGASW-UHFFFAOYSA-N Glycolic acid Chemical compound OCC(O)=O AEMRFAOFKBGASW-UHFFFAOYSA-N 0.000 description 2
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- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 description 2
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Landscapes
- Macromonomer-Based Addition Polymer (AREA)
- Coating Of Shaped Articles Made Of Macromolecular Substances (AREA)
- Polymerisation Methods In General (AREA)
- Graft Or Block Polymers (AREA)
- Laminated Bodies (AREA)
- Paints Or Removers (AREA)
Abstract
Description
本発明は、優れた防眩性と延伸性を有するハードコート層を形成し得る硬化性重合体組成物及びその硬化塗膜を有する積層体に関する。 The present invention relates to a curable polymer composition capable of forming a hard coat layer having excellent antiglare properties and stretchability, and a laminate having the cured coating film.
タッチパネルディスプレイ等の画像表示装置の表面に防眩性を付与する技術として、表面に微細な凹凸を有するフィルムを、ディスプレイ等の樹脂成形体を成形するのと同時に、インサート成形する方法が知られている。
たとえば特許文献１には、ＳＰ値（溶解性パラメータ）の異なる２種の重合体を含む組成物により、表面に凹凸を発現させた防眩性フィルムが記載されている。
As a technique for imparting antiglare properties to the surface of an image display device such as a touch panel display, a method of insert molding a film having fine irregularities on the surface and molding a resin molded body such as a display is known. Yes.
For example, Patent Document 1 describes an antiglare film having irregularities on its surface by a composition containing two types of polymers having different SP values (solubility parameters).
しかし特許文献１記載の方法は、成形加工の際の延伸性が不十分であり、表面の耐擦傷性も不十分であった。
本発明はこれらの問題を解決することを目的とする。
However, the method described in Patent Document 1 has insufficient stretchability during the molding process and also has insufficient surface scratch resistance.
The present invention aims to solve these problems.
即ち、本発明は以下の［１］〜［９］を要旨とする。 That is, the gist of the present invention is the following [1] to [9].
［１］重合体Ａ、前記重合体Ａと溶解度パラメータ（ＳＰ値）が異なり前記重合体Ａに非相溶性の重合体Ｂ及び多官能（メタ）アクリレートＣを含む硬化性重合体組成物であって、以下の（１）、（２）を満足する硬化性重合体組成物。
（１）ＳＰＡ−ＳＰＢ≧０．５
（２）重合体Ａが不飽和二重結合を有し、二重結合当量が０．１ｍｍｏｌ／ｇ以上４ｍｍｏｌ／ｇ以下
（ＳＰＡ、ＳＰＢはそれぞれ、前記重合体Ａ、前記重合体Ｂの溶解度パラメータを示す。）
[２]以下の（３）を満足する［１］に記載の硬化性重合体組成物。
（３）ＳＰＣ−ＳＰＢ≦(ＳＰＡ−ＳＰＣ)×２．５
（ＳＰＣは前記多官能（メタ）アクリレートＣの溶解度パラメータを示す。）
［３］前記重合体Ａの重量平均分子量が２，０００より大きく２００，０００以下である［１］又は［２］に記載の硬化性重合体組成物。
［４］前記重合体Ｂの重量平均分子量が２，０００より大きく２００，０００以下である［１］〜［３］のいずれか１項に記載の硬化性重合体組成物。
［５］前記重合体Ａ，重合体Ｂの両方に良溶媒である有機溶媒（溶媒Ｘ）と、重合体Ａに対しては良溶媒であるが、重合体Ｂに対しては貧溶媒である有機溶媒（溶媒Ｙ）を含む［１］〜［４］のいずれか１項に記載の硬化性重合体組成物。
［６］前記硬化性重合体組成物１００質量部中の重合体Ａの含有量が３０〜９０質量部、重合体Ｂの含有量が５〜４０質量部、多官能（メタ）アクリレートＣの含有量が１〜４９質量部である［１］〜［５］のいずれか１項に記載の硬化性重合体組成物。
［７］前記硬化性重合体組成物を硬化させた硬化塗膜を延伸率１００％に延伸させた時の延伸前後の６０°光沢度変化値が３０以下である［１］〜［６］のいずれか１項に記載の硬化性重合体組成物の硬化塗膜を有する積層体。
［８］前記硬化性重合体組成物を硬化させた硬化塗膜のクラックを生じる延伸率が５０％以上である［１］〜［６］のいずれか１項に記載の硬化性重合体組成物の硬化塗膜を有する積層体。
［９］［１］〜［６］のいずれか１項に記載の硬化性重合体組成物の硬化塗膜を有する積層体。
[1] A curable polymer composition comprising a polymer A, a solubility parameter (SP value) different from that of the polymer A, and an incompatible polymer B and polyfunctional (meth) acrylate C. A curable polymer composition satisfying the following (1) and (2).
(1) SPA-SPB ≧ 0.5
(2) Polymer A has an unsaturated double bond, and the double bond equivalent is 0.1 mmol / g or more and 4 mmol / g or less (SPA and SPB are the solubility parameters of Polymer A and Polymer B, respectively) Is shown.)
[2] The curable polymer composition according to [1], which satisfies the following (3).
(3) SPC-SPB ≦ (SPA-SPC) × 2.5
(SPC indicates the solubility parameter of the polyfunctional (meth) acrylate C)
[3] The curable polymer composition according to [1] or [2], wherein the polymer A has a weight average molecular weight of more than 2,000 and 200,000 or less.
[4] The curable polymer composition according to any one of [1] to [3], wherein the polymer B has a weight average molecular weight of more than 2,000 and 200,000 or less.
[5] An organic solvent (solvent X) that is a good solvent for both the polymer A and the polymer B and a good solvent for the polymer A, but a poor solvent for the polymer B The curable polymer composition according to any one of [1] to [4], which contains an organic solvent (solvent Y).
[6] The content of the polymer A in 100 parts by mass of the curable polymer composition is 30 to 90 parts by mass, the content of the polymer B is 5 to 40 parts by mass, and the polyfunctional (meth) acrylate C is contained. The curable polymer composition according to any one of [1] to [5], wherein the amount is 1 to 49 parts by mass.
[7] The [60] gloss change value before and after stretching when a cured coating film obtained by curing the curable polymer composition is stretched to 100% is 30 or less. The laminated body which has a cured coating film of the curable polymer composition of any one.
[8] The curable polymer composition according to any one of [1] to [6], wherein a stretch ratio causing cracks in the cured coating film obtained by curing the curable polymer composition is 50% or more. A laminate having a cured coating film.
[9] A laminate having a cured coating film of the curable polymer composition according to any one of [1] to [6].
本発明によれば、優れた防眩性と延伸性を有するハードコート層を形成し得る硬化性重合体組成物及びその硬化塗膜を有する積層体を提供することができる。 According to the present invention, it is possible to provide a curable polymer composition capable of forming a hard coat layer having excellent antiglare properties and stretchability, and a laminate having the cured coating film.
本発明の硬化性重合体組成物は、重合体Ａ、前記重合体Ａと溶解度パラメータ（ＳＰ値）が異なり前記重合体Ａに非相溶性の重合体Ｂ及び多官能（メタ）アクリレートＣを含む硬化性重合体組成物であって、以下の（１）〜（２）を満足する。
（１）ＳＰＡ−ＳＰＢ≧０．５
（２）重合体Ａが不飽和二重結合を有し、二重結合当量が０．１ｍｍｏｌ／ｇ以上４ｍｍｏｌ／ｇ以下
（ＳＰＡ、ＳＰＢはそれぞれ、前記重合体Ａ、前記重合体Ｂの溶解度パラメータを示す。）
The curable polymer composition of the present invention includes a polymer A, a solubility parameter (SP value) different from that of the polymer A, and a polymer B that is incompatible with the polymer A and a polyfunctional (meth) acrylate C. The curable polymer composition satisfies the following (1) to (2).
(1) SPA-SPB ≧ 0.5
(2) Polymer A has an unsaturated double bond, and the double bond equivalent is 0.1 mmol / g or more and 4 mmol / g or less (SPA and SPB are the solubility parameters of Polymer A and Polymer B, respectively) Is shown.)
本発明において、重合体Ａと重合体Ｂは溶解度パラメータ（ＳＰ値）が異なり、重合体Ａと重合体Ｂは非相溶性となることが必要である。非相溶性とは相互に溶解しないことを意味する。本発明では重合体Ａと重合体Ｂが非相溶性であるために相分離し、本発明の硬化性重合体組成物を含む硬化物の表面に微細な凹凸が形成され、防眩性が発現する。 In the present invention, the polymer A and the polymer B have different solubility parameters (SP values), and the polymer A and the polymer B need to be incompatible. Incompatible means not soluble in each other. In the present invention, since the polymer A and the polymer B are incompatible, they are phase-separated, and fine irregularities are formed on the surface of the cured product containing the curable polymer composition of the present invention, thereby exhibiting antiglare properties. To do.
本発明ではＳＰＡ−ＳＰＢ≧０．５を満足することにより、重合体Ａが凹部、重合体Ｂが凸部を構成する。ＳＰＡとＳＰＢの差が０．５未満では重合体Ａと重合体Ｂが相溶性となり、本発明の硬化性重合体組成物の硬化塗膜を形成する際に凹凸形成がされにくくなって防眩性が発現しにくくなる。ＳＰＡとＳＰＢの差は、防眩性発現の点で０．８以上が好ましく、１．５以上がより好ましく、２．０以上が特に好ましい。 In the present invention, by satisfying SPA-SPB ≧ 0.5, the polymer A constitutes a concave portion and the polymer B constitutes a convex portion. When the difference between SPA and SPB is less than 0.5, the polymer A and the polymer B become compatible, and it becomes difficult to form irregularities when forming a cured coating film of the curable polymer composition of the present invention, thus preventing glare. Sex becomes difficult to express. The difference between SPA and SPB is preferably 0.8 or more, more preferably 1.5 or more, and particularly preferably 2.0 or more in terms of antiglare properties.
なお、ＳＰＢをＳＰＡより低くするためには、例えば、前記重合体Ａの側鎖に極性が高い官能基を多く含むようにすればよい。側鎖に極性が高い官能基を導入する方法としては、例えば、２−ヒドロキシエチル（メタ）アクリレートや、２−ヒドロキシプロピル（メタ）アクリレート、４−ヒドロキシブチル（メタ）アクリレート等の高極性（メタ）アクリレート系単量体や、ジメチルアクリルアミドや、ヒドロキシエチルアクリルアミド、アクロイルモルホリン等の高極性アクリルアミド系単量体を共重合する方法が挙げられる。また、グリシジル（メタ）アクリレート、β−メチルグルシジル（メタ）アクリレート、３,４-エポキシシクロヘキシルメチル（メタ)アクリレート、４-ヒドロキシブチル（メタ）アクリレートグリシジルエーテル等のエポキシ基を有する（メタ）アクリル酸エステル単量体を共重合した後に、（メタ）アクリル酸、グリコール酸、ジメチロールプロピオン酸等の不飽和カルボン酸類を付加することで水酸基を導入する方法が挙げられる。 In order to make SPB lower than SPA, for example, the side chain of the polymer A may contain many functional groups having high polarity. Examples of the method for introducing a highly polar functional group into the side chain include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, ) A method of copolymerizing a highly polar acrylamide monomer such as an acrylate monomer, dimethylacrylamide, hydroxyethylacrylamide, acroylmorpholine, or the like. In addition, (meth) acryl having an epoxy group such as glycidyl (meth) acrylate, β-methyl glycidyl (meth) acrylate, 3,4-epoxycyclohexylmethyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate glycidyl ether, etc. A method of introducing a hydroxyl group by adding an unsaturated carboxylic acid such as (meth) acrylic acid, glycolic acid, dimethylolpropionic acid, etc. after copolymerizing the acid ester monomer.
また本発明では、重合体Ａが不飽和二重結合を有し、二重結合当量が０．１ｍｍｏｌ／ｇ以上４ｍｍｏｌ／ｇ以下であることが必要である。前記二重結合当量が０．１ｍｍｏｌ／ｇ未満では、本発明の硬化性重合体組成物から得られた硬化物の耐擦傷性が不十分となり、４ｍｍｏｌ／ｇを超えると、重合体Ａの架橋密度が高くなり延伸性が不十分となる。
前記、不飽和二重結合当量は、１ｍｍｏｌ／ｇ以上３ｍｍｏｌ／ｇ以下が好ましく、１．２ｍｍｏｌ／ｇ以上２．５ｍｍｏｌ／ｇ以下がより好ましい。
In the present invention, it is necessary that the polymer A has an unsaturated double bond and the double bond equivalent is 0.1 mmol / g or more and 4 mmol / g or less. When the double bond equivalent is less than 0.1 mmol / g, the scratch resistance of the cured product obtained from the curable polymer composition of the present invention is insufficient, and when it exceeds 4 mmol / g, the polymer A is crosslinked. The density becomes high and the stretchability becomes insufficient.
The unsaturated double bond equivalent is preferably 1 mmol / g or more and 3 mmol / g or less, and more preferably 1.2 mmol / g or more and 2.5 mmol / g or less.
更に本発明では、耐擦傷性の向上の観点から、多官能（メタ）アクリレートを含むことが好ましい。多官能（メタ）アクリレートＣのＳＰ値（ＳＰＣ）が、重合体ＡのＳＰ値（ＳＰＡ）及び重合体Ｃ（ＳＰＣ）のＳＰ値との関係において、ＳＰＣ−ＳＰＢ≦(ＳＰＡ−ＳＰＣ)×２．５を満足することが好ましい。本条件を満足することにより、多官能（メタ）アクリレートＣが凸部となる前記重合体Ｂへの親和性が高くなり、凸部の架橋密度が上がり耐擦傷性が向上する。 Furthermore, in this invention, it is preferable that a polyfunctional (meth) acrylate is included from a viewpoint of an improvement of abrasion resistance. In the relationship between the SP value (SPC) of the polyfunctional (meth) acrylate C and the SP value of the polymer A (SPA) and the SP value of the polymer C (SPC), SPC-SPB ≦ (SPA-SPC) × 2 .5 is preferably satisfied. By satisfying this condition, the affinity for the polymer B in which the polyfunctional (meth) acrylate C becomes a convex portion is increased, the crosslink density of the convex portion is increased, and the scratch resistance is improved.
なお本発明において、溶解度パラメータ（ＳＰ値）は次の方法により実測される値である。
サンプル０．５ｇを１００ｍｌ三角フラスコに秤量し、プロピレングリコールモノメチルエーテル１０ｍｌを加えて樹脂を溶解させる。ここへ、マグネチックスターラーで攪拌しながら、ヘキサンを滴下していき、溶液に濁りが生じた点（濁点）のヘキサンの滴下量（ｖｈ）を求める。次に、ヘキサンの代わりに脱イオン水を使用したときの、濁点における脱イオン水の滴下量（ｖｄ）を求める。
ｖｈ、ｖｄより、ＳＰ値は参考文献：ＳＵＨ、ＣＬＡＲＫＥ、Ｊ．Ｐ．Ｓ．Ａ−１、５、１６７１〜１６８１（１９６７）により示された式を用いて求めることができる。また、ＳＰＣは、上記のＳＰＡ及びＳＰＣの測定方法において、プロピレングリコールモノメチルエーテルの代わりにアセトンを使用して求めるものとする。
なお、サンプルがプロピレングリコールモノメチルエーテルやアセトンに溶解しない等、溶解性パラメーターが上記の方法により求めることができない場合には、Ｆｅｄｏｒｓらが提案した方法によって計算する。具体的には「ＰＯＬＹＭＥＲ ＥＮＧＩＮＥＥＲＩＮＧ ＡＮＤ ＳＣＩＥＮＣＥ，ＦＥＢＲＵＡＲＹ，１９７４，Ｖｏｌ．１４，Ｎｏ．２，ＲＯＢＥＲＴ Ｆ．ＦＥＤＯＲＳ．（１４７〜１５４頁）」を参照して求めることができる。
In the present invention, the solubility parameter (SP value) is a value measured by the following method.
0.5 g of sample is weighed into a 100 ml Erlenmeyer flask, and 10 ml of propylene glycol monomethyl ether is added to dissolve the resin. Here, hexane is dropped while stirring with a magnetic stirrer, and the dripping amount (vh) of hexane at the point where the solution becomes cloudy (turbid point) is determined. Next, when deionized water is used instead of hexane, the dripping amount (vd) of deionized water at the cloud point is obtained.
From vh and vd, the SP value is given in References: SUH, CLARKE, J. P. S. A-1, 5, 1671-1681 (1967). In addition, SPC is obtained by using acetone in place of propylene glycol monomethyl ether in the SPA and SPC measurement methods described above.
When the solubility parameter cannot be obtained by the above method, for example, the sample does not dissolve in propylene glycol monomethyl ether or acetone, the calculation is performed by the method proposed by Fedors et al. Specifically, it can be obtained by referring to “POLYMER ENGINEERING AND SCIENCE, FEBRUARY, 1974, Vol. 14, No. 2, ROBERT F. FEDORS. (Pp. 147 to 154)”.
また本発明では、重合体Ａと重合体Ｂのガラス転移温度の差（ΔＴｇ＝ＴｇＢ−ＴｇＡ）がΔＴｇ＜４０℃であるのが好ましく、ΔＴｇ＜２０℃であるのが更に好ましい。重合体Ａと重合体Ｂのガラス転移温度の差を小さくすることで、本発明の硬化性重合体組成物の硬化物を延伸した場合に、前記硬化物全体が均一に延伸され、延伸前後の凸部面積と凹部面積の比率が大きく変わることを抑制し、延伸前後の光沢変化を少なくすることができる。 In the present invention, the difference in glass transition temperature between polymer A and polymer B (ΔTg = TgB−TgA) is preferably ΔTg <40 ° C., more preferably ΔTg <20 ° C. By reducing the difference in glass transition temperature between the polymer A and the polymer B, when the cured product of the curable polymer composition of the present invention is stretched, the entire cured product is stretched uniformly, before and after stretching. It can suppress that the ratio of a convex part area and a recessed part area changes greatly, and can reduce the gloss change before and behind extending | stretching.
＜重合体Ａ＞
本発明において重合体Ａは、本発明の硬化性重合体組成物を含む硬化物の凹部を構成する。
前記重合体Ａは、不飽和二重結合を有していることが必要である。不飽和二重結合を有する重合体Ａは、例えば、あらかじめ、エポキシ基を有する単量体と脂肪族の単量体を共重合した後に、不飽和二重結合とカルボキシル基の両方を含む単量体により開環付加させることで製造することができる。
前記エポキシ基を有する単量体としてはグリシジル（メタ）アクリレート、β−メチルグルシジル（メタ）アクリレート、３,４-エポキシシクロヘキシルメチル（メタ)アクリレート、４-ヒドロキシブチル（メタ）アクリレートグリシジルエーテル等がある。エポキシ基の開環付加反応性が良好である点でグリシジル（メタ）アクリレート好ましい。
前記脂肪族の単量体としてはメチル（メタ）アクリレート、エチル（メタ）アクリレート、ｎ−プロピル（メタ）アクリレート、ｉ−プロピル（メタ）アクリレート、ｎ−ブチル（メタ）アクリレート、ｉ−ブチル（メタ）アクリレート、ｔ−ブチル（メタ）アクリレート、ｎ−ペンチル（メタ）アクリレート、ｉ−ペンチル（メタ）アクリレート、ｎ−へキシル（メタ）アクリレート、ｎ−オクチル（メタ）アクリレート、２−エチルへキシル（メタ）アクリレート、ラウリル（メタ）アクリレート、シクロヘキシル（メタ）アクリレート、イソボルニル（メタ）アクリレート、ジシクロペンテニルオキシエチル（メタ）アクリレート、ジシクロペンタニル（メタ）アクリレート等の（メタ）アクリル酸エステル；２−ヒドロキシエチル（メタ）アクリレート、２−ヒドロキシプロピル（メタ）アクリレート、３−ヒドロキシプロピル（メタ）アクリレート、４−ヒドロキシブチル（メタ）アクリレート等の水酸基含有（メタ）アクリル酸エステル；フェノキシ（メタ）アクリレート、ベンジル（メタ）アクリレート、フェノキシエチル（メタ）アクリレート、フェノキシポリエチレングリコール（メタ）アクリレート、２−ヒドロキシ−３−フェノキシプロピル（メタ）アクリレート、ｏ−ビフェニルオキシエチル（メタ）アクリレート等の芳香族環含有（メタ）アクリル酸エステル；（メタ）アクリルイソシアネート、２−（メタ）アクリロイルオキシエチルイソシアネート等のイソシアネート基含有（メタ）アクリル酸エステルが挙げられる。
前記（メタ）アクリル系単量体の中でも、良好な硬化性を発揮させる点で、メチル（メタ）アクリレート、エチル（メタ）アクリレート、２−ヒドロキシエチル（メタ）アクリレート、（メタ）アクリロイルモルフォリン、イソボルニル（メタ）アクリレート、ベンジル（メタ）アクリレート、ｏ−ビフェニルオキシエチル（メタ）アクリレートが好ましい。
不飽和二重結合とカルボキシル基の両方を含む単量体としては（メタ）アクリル酸、イタコン酸、２−アクリロイルオキシエチルサクシネート、２−メタクリロイルオキシエチルサクシネート、２，２，２，−トリスアクリロイルオキシメチルエチルフタル酸等が挙げられる。
これらの中でも、活性エネルギー線による硬化性が良好である点で（メタ）アクリル酸が好ましい。
なお、本発明において、（メタ）アクリルは、アクリル又はメタクリルを意味する。
<Polymer A>
In this invention, the polymer A comprises the recessed part of the hardened | cured material containing the curable polymer composition of this invention.
The polymer A needs to have an unsaturated double bond. The polymer A having an unsaturated double bond is, for example, a monomer comprising both an unsaturated double bond and a carboxyl group after copolymerizing an epoxy group-containing monomer and an aliphatic monomer in advance. It can be produced by ring-opening addition by the body.
Examples of the monomer having an epoxy group include glycidyl (meth) acrylate, β-methylglycidyl (meth) acrylate, 3,4-epoxycyclohexylmethyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate glycidyl ether, and the like. is there. Glycidyl (meth) acrylate is preferable in that the ring-opening addition reactivity of the epoxy group is good.
Examples of the aliphatic monomer include methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, i-propyl (meth) acrylate, n-butyl (meth) acrylate, i-butyl (meth) ) Acrylate, t-butyl (meth) acrylate, n-pentyl (meth) acrylate, i-pentyl (meth) acrylate, n-hexyl (meth) acrylate, n-octyl (meth) acrylate, 2-ethylhexyl ( (Meth) acrylates such as (meth) acrylate, lauryl (meth) acrylate, cyclohexyl (meth) acrylate, isobornyl (meth) acrylate, dicyclopentenyloxyethyl (meth) acrylate, dicyclopentanyl (meth) acrylate; 2 -Hydroxyethyl ( ) Acrylate, 2-hydroxypropyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, hydroxyl group-containing (meth) acrylate such as 4-hydroxybutyl (meth) acrylate; phenoxy (meth) acrylate, benzyl (meth) ) Acrylic ring-containing (meth) acrylic such as acrylate, phenoxyethyl (meth) acrylate, phenoxypolyethylene glycol (meth) acrylate, 2-hydroxy-3-phenoxypropyl (meth) acrylate, o-biphenyloxyethyl (meth) acrylate, etc. Acid ester; isocyanate group-containing (meth) acrylic acid ester such as (meth) acrylic isocyanate and 2- (meth) acryloyloxyethyl isocyanate.
Among the (meth) acrylic monomers, methyl (meth) acrylate, ethyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, (meth) acryloylmorpholine, Isobornyl (meth) acrylate, benzyl (meth) acrylate, and o-biphenyloxyethyl (meth) acrylate are preferred.
Monomers containing both unsaturated double bonds and carboxyl groups include (meth) acrylic acid, itaconic acid, 2-acryloyloxyethyl succinate, 2-methacryloyloxyethyl succinate, 2,2,2, -tris Examples include acryloyloxymethylethylphthalic acid.
Among these, (meth) acrylic acid is preferable in terms of good curability by active energy rays.
In the present invention, (meth) acryl means acryl or methacryl.
更に本発明では、硬化塗膜の耐擦傷性を向上する点で、前記重合体Ａの重量平均分子量は、２，０００より大きく２００，０００以下が好ましく、６，０００より大きく１５０，０００以下がより好ましく４０，０００より大きく１００，０００以下が特に好ましい。なお、前記重量体Ａの重量平均分子量はゲルパーミエーションクロマトグラフィー法（ＧＰＣ法）により測定した標準ポリスチレン換算よる値である。 Further, in the present invention, the weight average molecular weight of the polymer A is preferably more than 2,000 and not more than 200,000, more preferably more than 6,000 and not more than 150,000 in terms of improving the scratch resistance of the cured coating film. More preferably, it is more than 40,000 and 100,000 or less. In addition, the weight average molecular weight of the said weight body A is the value by standard polystyrene conversion measured by the gel permeation chromatography method (GPC method).
また本発明において、硬化性を良好にする点で、前記重合体Ａの含有量は硬化性重合体組成物１００質量部に対し３０〜９０質量部が好ましく、４０〜８５質量部がより好ましく、５０〜８０質量部がより好ましい。 Moreover, in this invention, 30-90 mass parts is preferable with respect to 100 mass parts of curable polymer compositions, and 40-85 mass parts is more preferable at the point which makes sclerosis | hardenability favorable, 50-80 mass parts is more preferable.
＜重合体Ｂ＞
本発明において重合体Ｂは、本発明の硬化性重合体組成物を含む硬化物の凸部を構成する。
前記重合体Ｂを構成する単量体としては、スチレン、ｏ−メチルスチレン、ｍ−メチルスチレン、ｐ−メチルスチレン、α−メチルスチレン、ｐ−エチルスチレン、２，４−ジメチルスチレン、ｐ−ｎ−ブチルスチレン、ｐ−ｔ−ブチルスチレン、ｐ−ｎ−ヘキシルスチレン、ｐ−ｎ−オクチルスチレン、ｐ−ｎ−ノニルスチレン、ｐ−ｎ−テンシルスチレン、ｐ−ｎ−ドデシルスチレン、ｐ−フェニルスチレン、３，４−ジシクロシルスチレン等のスチレン系単量体や、メチル（メタ）アクリレート、エチル（メタ）アクリレート、ｎ−プロピル（メタ）アクリレート、ｉ−プロピル（メタ）アクリレート、ｎ−ブチル（メタ）アクリレート、ｉ−ブチル（メタ）アクリレート、ｔ−ブチル（メタ）アクリレート、ｎ−ペンチル（メタ）アクリレート、ｉ−ペンチル（メタ）アクリレート、ｎ−へキシル（メタ）アクリレート、ｎ−オクチル（メタ）アクリレート、２−エチルへキシル（メタ）アクリレート、ラウリル（メタ）アクリレート、シクロヘキシル（メタ）アクリレート、イソボルニル（メタ）アクリレート、ジシクロペンテニルオキシエチル（メタ）アクリレート、ジシクロペンタニル（メタ）アクリレート等の（メタ）アクリル酸エステル系単量体が挙げられる。
これらの中でも、ＳＰ値を低下させやすく、良好な防眩性を発現する点からスチレン、メチル（メタ）アクリレート、シクロヘキシル（メタ）アクリレート、イソボルニル（メタ）アクリレート、ジシクロペンテニルオキシエチル（メタ）アクリレート、ジシクロペンタニル（メタ）アクリレート等が好ましい。
<Polymer B>
In this invention, the polymer B comprises the convex part of the hardened | cured material containing the curable polymer composition of this invention.
Examples of the monomer constituting the polymer B include styrene, o-methylstyrene, m-methylstyrene, p-methylstyrene, α-methylstyrene, p-ethylstyrene, 2,4-dimethylstyrene, and pn. -Butyl styrene, pt-butyl styrene, pn-hexyl styrene, pn-octyl styrene, pn-nonyl styrene, pn-tensyl styrene, pn-dodecyl styrene, p-phenyl Styrene monomers such as styrene and 3,4-dicyclosyl styrene, methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, i-propyl (meth) acrylate, n-butyl (Meth) acrylate, i-butyl (meth) acrylate, t-butyl (meth) acrylate, n-pentyl (meth) a Relate, i-pentyl (meth) acrylate, n-hexyl (meth) acrylate, n-octyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, lauryl (meth) acrylate, cyclohexyl (meth) acrylate, isobornyl Examples include (meth) acrylate monomers such as (meth) acrylate, dicyclopentenyloxyethyl (meth) acrylate, and dicyclopentanyl (meth) acrylate.
Among these, styrene, methyl (meth) acrylate, cyclohexyl (meth) acrylate, isobornyl (meth) acrylate, dicyclopentenyloxyethyl (meth) acrylate are easy to lower the SP value and express good antiglare properties. Dicyclopentanyl (meth) acrylate and the like are preferable.
また本発明では、硬化塗膜の耐傷付性を向上する点で、前記重合体Ｂの重量平均分子量は２，０００より大きく２００，０００以下が好ましく、６，０００より大きく１５０，０００以下がより好ましく４０，０００より大きく１００，０００以下が特に好ましい。
なお、前記重量体Ｂの平均分子量はゲルパーミエーションクロマトグラフィー法（ＧＰＣ法）により測定した標準ポリスチレン換算よる値である。
In the present invention, the weight average molecular weight of the polymer B is preferably more than 2,000 and not more than 200,000, more preferably more than 6,000 and not more than 150,000 in terms of improving the scratch resistance of the cured coating film. It is preferably more than 40,000 and 100,000 or less.
In addition, the average molecular weight of the said weight body B is the value by standard polystyrene conversion measured by the gel permeation chromatography method (GPC method).
前記重合体Ｂは光重合法、懸濁重合法等の一般的な重合法によって製造することができる。 The polymer B can be produced by a general polymerization method such as a photopolymerization method or a suspension polymerization method.
また本発明において、硬化性重合体組成物の防眩性と透明性の両立の点で、前記重合体Ｂの含有量は、硬化性重合体組成物１００質量部に対し５〜４０質量部が好ましく、１５〜３０質量部がより好ましい。 Moreover, in this invention, content of the said polymer B is 5-40 mass parts with respect to 100 mass parts of curable polymer compositions by the point of coexistence of the glare-proof property and transparency of a curable polymer composition. Preferably, 15 to 30 parts by mass are more preferable.
＜多官能（メタ）アクリレートＣ＞
本発明において多官能（メタ）アクリレートＣとは（メタ）アクリロイル基を有し、一分子中に２つ以上の不飽和二重結合を有する化合物で、多価アルコールと（メタ）アクリレートとの脱アルコール反応物、ウレタン（メタ）アクリレートオリゴマー、ポリエステル（メタ）アクリレートオリゴマー、前記重合体Ｂで挙げられた樹脂の低分子量物、ペンタエリスリトールトリ（メタ）アクリレート、ペンタエリスリトールテトラ（メタ）アクリレート、ジペンタエリスリトールヘキサ（メタ）アクリレート、ジペンタエリスリトールペンタ（メタ）アクリレート、トリメチロールプロパントリ（メタ）アクリレート等が挙げられる。これらの中でも得られる硬化物の耐傷付性が高い又は硬化性が良好な点でウレタン（メタ）アクリレートオリゴマー、ポリエステル（メタ）アクリレートオリゴマー、ペンタエリスリトールテトラ（メタ）アクリレート、ジペンタエリスリトールヘキサ（メタ）アクリレート、ジペンタエリスリトールペンタ（メタ）アクリレートが好ましい。
<Multifunctional (meth) acrylate C>
In the present invention, the polyfunctional (meth) acrylate C is a compound having a (meth) acryloyl group and having two or more unsaturated double bonds in one molecule, and is a dehydration of polyhydric alcohol and (meth) acrylate. Alcohol reaction product, urethane (meth) acrylate oligomer, polyester (meth) acrylate oligomer, low molecular weight resin of the above-mentioned polymer B, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipenta Examples include erythritol hexa (meth) acrylate, dipentaerythritol penta (meth) acrylate, and trimethylolpropane tri (meth) acrylate. Among these, urethane (meth) acrylate oligomer, polyester (meth) acrylate oligomer, pentaerythritol tetra (meth) acrylate, dipentaerythritol hexa (meth) are high in scratch resistance of cured products or good curability. Preferred are acrylate and dipentaerythritol penta (meth) acrylate.
また本発明において、延伸性と耐傷付性を両立する点で、前記多官能（メタ）アクリレートＣの含有量は、硬化性重合体組成物１００質量部に対し１〜４９質量部が好ましく、１５〜４０質量部がより好ましく、２５〜３５質量部が更に好ましい。 In the present invention, the content of the polyfunctional (meth) acrylate C is preferably 1 to 49 parts by mass with respect to 100 parts by mass of the curable polymer composition in terms of achieving both stretchability and scratch resistance. -40 mass parts is more preferable, and 25-35 mass parts is still more preferable.
＜硬化性重合体組成物＞
本発明の硬化性重合体組成物は有機溶媒、重合開始剤、レべリング剤、無機粒子、その他の成分を含んでいてもよい。
<Curable polymer composition>
The curable polymer composition of the present invention may contain an organic solvent, a polymerization initiator, a leveling agent, inorganic particles, and other components.
＜有機溶媒＞
本発明の硬化性重合体組成物は、重合体Ａ，重合体Ｂの両方に良溶媒である有機溶媒（溶媒Ｘ）と、重合体Ａに対しては良溶媒であるが、重合体Ｂに対しては貧溶媒である有機溶媒（溶媒Ｙ）の両方を含有することが好ましい。前記有機溶媒を含有させることで硬化性重合体組成物の塗布作業における作業性と、硬化塗膜の防眩性が向上する。
<Organic solvent>
The curable polymer composition of the present invention is an organic solvent (solvent X) that is a good solvent for both the polymer A and the polymer B, and a good solvent for the polymer A. On the other hand, it is preferable to contain both the organic solvent (solvent Y) which is a poor solvent. By containing the organic solvent, the workability in the application work of the curable polymer composition and the antiglare property of the cured coating film are improved.
＜溶剤Ｘ＞
溶剤Ｘとしては、例えば、アセトン、メチルエチルケトン、メチルプロピルケトン、メチルイソブチルケトン、ジイソブチルケトン、シクロヘキサノン、ジアセトンアルコール等のケトン系溶媒；ペンタノール、ヘキサノール、ヘプタノール、オクタノール等のアルコール系溶媒；エチレングリコールモノエチルエーテル、エチレングリコールモノブチルエーテル、エチレングリコールモノエチルエーテルアセテート、プロピレングリコールモノメチルエーテルアセテート等のエーテル系溶媒；酢酸メチル、酢酸エチル、酢酸ブチル、酢酸メトキシブチル、酢酸アミル、酢酸プロピル、乳酸エチル、乳酸メチル、乳酸ブチル等のエステル系溶媒；トルエン、キシレン、ソルベントナフサ等の炭化水素系溶媒が挙げられる。
<Solvent X>
Examples of the solvent X include ketone solvents such as acetone, methyl ethyl ketone, methyl propyl ketone, methyl isobutyl ketone, diisobutyl ketone, cyclohexanone and diacetone alcohol; alcohol solvents such as pentanol, hexanol, heptanol and octanol; ethylene glycol mono Ether solvents such as ethyl ether, ethylene glycol monobutyl ether, ethylene glycol monoethyl ether acetate, propylene glycol monomethyl ether acetate; methyl acetate, ethyl acetate, butyl acetate, methoxybutyl acetate, amyl acetate, propyl acetate, ethyl lactate, methyl lactate And ester solvents such as butyl lactate; hydrocarbon solvents such as toluene, xylene and solvent naphtha.
＜溶剤Ｙ＞
溶剤Ｙは、重合体Ａに対しては良溶媒であり、重合体Ｂに対しては貧溶媒であるのが好ましい。重合体Ｂの貧溶媒であるとは、重合体Ｂが溶解しない溶媒であることを意味する。
溶剤Ｙとしては、例えば、メタノール、エタノール、ブタノール、イソブタノール、プロピルアルコール等のアルコール系溶媒；アセトン,メチルエチルケトン、メチルプロピルケトン 、メチルイソブチルケトン、ジイソブチルケトン、シクロヘキサノンジアセトンアルコール等のケトン系溶媒；ノルマルプロピルアルコールジエチレングリコールモノメチルエーテル、プロピレングリコールモノメチルエーテル等のエーテル系溶媒；酢酸メチル、酢酸エチル、酢酸ブチル、酢酸メトキシブチル、酢酸アミル、酢酸プロピル、乳酸エチル、乳酸メチル、乳酸ブチル等のエステル系溶媒；トルエン、キシレン、ソルベントナフサ、ヘキサン、シクロヘキサン、エチルシクロヘキサン、メチルシクロヘキサン、ヘプタン、オクタン、デカン等の炭化水素系溶媒等が挙げられる。
<Solvent Y>
The solvent Y is preferably a good solvent for the polymer A and a poor solvent for the polymer B. The poor solvent for the polymer B means that the polymer B is a solvent that does not dissolve.
Examples of the solvent Y include alcohol solvents such as methanol, ethanol, butanol, isobutanol, and propyl alcohol; ketone solvents such as acetone, methyl ethyl ketone, methyl propyl ketone, methyl isobutyl ketone, diisobutyl ketone, and cyclohexanone diacetone alcohol; Ether solvents such as propyl alcohol diethylene glycol monomethyl ether and propylene glycol monomethyl ether; ester solvents such as methyl acetate, ethyl acetate, butyl acetate, methoxybutyl acetate, amyl acetate, propyl acetate, ethyl lactate, methyl lactate and butyl lactate; toluene , Xylene, solvent naphtha, hexane, cyclohexane, ethylcyclohexane, methylcyclohexane, heptane, octane, decane, etc. Based solvents and the like.
＜光重合開始剤＞
本発明の硬化性重合体組成物は、光重合開始剤を含有することが好ましい。
光重合開始剤としては、２−ヒドロキシ−２−メチル−１−フェニル−プロパン−１−オン、１−ヒドロキシ−シクロヘキシル−フェニル−ケトン、２−メチル−１−［４−（メチルチオ）フェニル］−２−モルフォリノプロパン−１−オン、２，２−ジメトキシ−１，２−ジフェニルエタン−１−オン、２−ベンジル−２−ジメチルアミノ−１−（４−モルフォリノフェニル）−ブタンノン−１等が挙げられる。これらの重合開始剤は１種を単独で用いてもよく、２種以上を混合して用いてもよい。
<Photopolymerization initiator>
The curable polymer composition of the present invention preferably contains a photopolymerization initiator.
As photopolymerization initiators, 2-hydroxy-2-methyl-1-phenyl-propan-1-one, 1-hydroxy-cyclohexyl-phenyl-ketone, 2-methyl-1- [4- (methylthio) phenyl]- 2-morpholinopropan-1-one, 2,2-dimethoxy-1,2-diphenylethane-1-one, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone-1, etc. Is mentioned. These polymerization initiators may be used alone or in a combination of two or more.
＜レべリング剤＞
本発明の重合体組成物は、レベリング剤を含有することが好ましい。レベリング剤の具体例を挙げると、アクリル系レベリング剤、シリコーン系レベリング剤、フッ素系レベリング剤等が挙げられる。
アクリル系レベリング剤としては、共栄社化学社製ポリフローシリーズを挙げることができる。
<Leveling agent>
The polymer composition of the present invention preferably contains a leveling agent. Specific examples of leveling agents include acrylic leveling agents, silicone leveling agents, and fluorine leveling agents.
As an acrylic leveling agent, Kyoeisha Chemical Co., Ltd. polyflow series can be mentioned.
シリコーン系レベリング剤としては、共栄社化学社製ポリフローシリーズ、ＢＹＫ Ｃｈｅｍｉｅ社製ＢＹＫシリーズ、日信化学工業社製シルフェイスＳＡＧシリーズ、東レダウコーニング社製ＦＧシリーズ、Ｌシリーズ、ＳＨシリーズ、ＳＦシリーズ、モメンティブ・パフォーマンス・マテリアルズ・ジャパン社製ＳＩＬＷＥＴＬ等を挙げることができる。 Silicone leveling agents include Kyoeisha Chemicals Polyflow Series, BYK Chemie BYK Series, Nissin Chemical Industry Silface SAG Series, Toray Dow Corning FG Series, L Series, SH Series, SF Series, Examples include SILWETL manufactured by Momentive Performance Materials Japan.
フッ素系レベリング剤としては、ＤＩＣ社製メガファックシリーズ、共栄社化学社製フローレンシリーズ、ネオス社製フタージェントシリーズ、ダイキン社製ＤＳＮ−４０３Ｎ、ＮＳ−９０１３等を挙げることができる。また、レベリング剤は１種のみで用いても２種以上を組み合わせて用いてもよい Examples of the fluorine leveling agent include DIC's Megafax series, Kyoeisha Chemical Co., Ltd., Floren series, Neos Co., Ltd.'s footgent series, Daikin's DSN-403N, NS-9013, and the like. Moreover, a leveling agent may be used only by 1 type, or may be used in combination of 2 or more type.
＜無機粒子＞
本発明の重合体組成物は、無機粒子を含有することが好ましい。
無機粒子としては、シリカ（オルガノシリカゾルを含む）、アルミナ、チタニア、ゼオライト、雲母、合成雲母、酸化カルシウム、酸化ジルコニウム、酸化亜鉛、フッ化マグネシウム、スメクタイト、合成スメクタイト、バーミキュライト、ＩＴＯ（酸化インジウム／酸化錫）、ＡＴＯ（酸化アンチモン／酸化錫）、酸化錫、酸化インジウム、酸化アンチモン等が挙げられ、これらの中でもシリカが好ましい。また、以上に挙げた無機粒子は１種のみを用いてもよく、２種以上を組み合わせて用いてもよい。
無機粒子は、硬度を向上させる点でシランカップリング剤で表面修飾された無機粒子として本発明の重合体組成物に配合されることが好ましい。
<Inorganic particles>
The polymer composition of the present invention preferably contains inorganic particles.
Inorganic particles include silica (including organosilica sol), alumina, titania, zeolite, mica, synthetic mica, calcium oxide, zirconium oxide, zinc oxide, magnesium fluoride, smectite, synthetic smectite, vermiculite, ITO (indium oxide / oxide) Tin), ATO (antimony oxide / tin oxide), tin oxide, indium oxide, antimony oxide and the like. Among these, silica is preferable. Moreover, the inorganic particle mentioned above may use only 1 type, and may be used in combination of 2 or more type.
The inorganic particles are preferably blended in the polymer composition of the present invention as inorganic particles whose surface is modified with a silane coupling agent in terms of improving hardness.
無機粒子の平均一次粒子径は通常、１μｍ以下であるが、２００ｎｍ以下であることが好ましく、１００ｎｍ以下であることがより好ましい。無機粒子の平均一次粒子径の下限値は特段限定されないが、通常５ｎｍ以上、好ましくは１０ｎｍ以上である。平均一次粒子径が１μｍを超える無機粒子を使用すると、粒子の自重により沈降が生じ硬化性重合体組成物の塗液の貯蔵安定性が低下しやすくなる。 The average primary particle diameter of the inorganic particles is usually 1 μm or less, preferably 200 nm or less, and more preferably 100 nm or less. The lower limit of the average primary particle diameter of the inorganic particles is not particularly limited, but is usually 5 nm or more, preferably 10 nm or more. When inorganic particles having an average primary particle diameter exceeding 1 μm are used, precipitation occurs due to the weight of the particles, and the storage stability of the coating liquid of the curable polymer composition tends to be lowered.
なお、本発明における無機粒子の平均一次粒子径は、例えば、ＴＥＭ等の電子顕微鏡により観察される粒子の大きさを平均した値をいう。 In addition, the average primary particle diameter of the inorganic particle in this invention says the value which averaged the magnitude | size of the particle | grains observed with electron microscopes, such as TEM.
＜その他の成分＞
本発明の硬化性重合体組成物は、本発明の効果を損なわない範囲で、チオール基を含有する化合物などの帯電防止剤、可塑剤、界面活性剤、酸化防止剤、紫外線吸収剤等を添加しても良い。
<Other ingredients>
In the curable polymer composition of the present invention, an antistatic agent such as a compound containing a thiol group, a plasticizer, a surfactant, an antioxidant, an ultraviolet absorber and the like are added within a range not impairing the effects of the present invention. You may do it.
本発明の硬化性重合体組成物は、一般的な混合機で各成分を混合することによって製造することができる。 The curable polymer composition of this invention can be manufactured by mixing each component with a common mixer.
＜硬化性重合体組成物の硬化物＞
本発明の硬化性重合体組成物の硬化物は、前記硬化性重合体組成物を基材に塗布した後、活性エネルギー線を照射し得られる。
<Hardened product of curable polymer composition>
The cured product of the curable polymer composition of the present invention can be obtained by irradiating active energy rays after applying the curable polymer composition to a substrate.
＜基材＞
本発明の硬化性重合体組成物を塗布、硬化させる基材フィルムは、特に限定するものではないが、例えば、ポリエチレンテレフタレート、ポリメチルメタクリレート、ポリカーボネート等の樹脂組成物からなる透明樹脂フィルムを用いることができる。
基材フィルムとしては、フィルムインサート成形品の耐熱性を向上させる点で、ガラス転移温度が高い樹脂を選定することが好ましい。
前記樹脂のガラス転移温度は１００℃以上１７０℃以下であることが好ましく、１２０℃以上１６０℃以下であることがより好ましく、１４０℃以上１５５℃以下であることが更に好ましい。前記フィルムインサート成形品が耐熱性を要求される前面パネルとして用いられる場合、例えば、ポリメチルメタクリレート、ポリカーボネート等を用いるのが好ましい。
基材フィルムは、全光線透過率８０％以上であることが好ましく、８５％以上であることがより好ましく、９０％以上であることが更に好ましい。
<Base material>
The base film on which the curable polymer composition of the present invention is applied and cured is not particularly limited. For example, a transparent resin film made of a resin composition such as polyethylene terephthalate, polymethyl methacrylate, or polycarbonate is used. Can do.
As the base film, it is preferable to select a resin having a high glass transition temperature in terms of improving the heat resistance of the film insert molded product.
The glass transition temperature of the resin is preferably 100 ° C. or higher and 170 ° C. or lower, more preferably 120 ° C. or higher and 160 ° C. or lower, and still more preferably 140 ° C. or higher and 155 ° C. or lower. When the film insert molded product is used as a front panel requiring heat resistance, for example, polymethyl methacrylate, polycarbonate, or the like is preferably used.
The base film preferably has a total light transmittance of 80% or more, more preferably 85% or more, and still more preferably 90% or more.
＜活性エネルギー線＞
本発明の硬化性重合体組成物は活性エネルギー線や加熱によって硬化させることができるが、硬化反応に要する時間を短縮できること、低温硬化ができ、防眩性表面を得やすい点で、活性エネルギー線が好ましい。
<Active energy rays>
The curable polymer composition of the present invention can be cured by active energy rays or heating, but it can reduce the time required for the curing reaction, can be cured at low temperature, and can easily obtain an antiglare surface. Is preferred.
組成物を硬化させる際に使用する活性エネルギー線としては、赤外線、可視光線、紫外線、Ｘ線、電子線、α線、β線、γ線等が挙げられる。装置コストや生産性の観点から電子線又は紫外線を利用することが好ましく、光源としては、電子線照射装置、超高圧水銀ランプ、高圧水銀ランプ、中圧水銀ランプ、低圧水銀ランプ、メタルハライドランプ、Ａｒレーザー、Ｈｅ−Ｃｄレーザー、固体レーザー、キセノンランプ、高周波誘導水銀ランプが好ましい。 Examples of active energy rays used for curing the composition include infrared rays, visible rays, ultraviolet rays, X-rays, electron beams, α rays, β rays, and γ rays. It is preferable to use an electron beam or an ultraviolet ray from the viewpoint of apparatus cost and productivity. As a light source, an electron beam irradiation apparatus, an ultrahigh pressure mercury lamp, a high pressure mercury lamp, a medium pressure mercury lamp, a low pressure mercury lamp, a metal halide lamp, Ar A laser, a He—Cd laser, a solid laser, a xenon lamp, and a high frequency induction mercury lamp are preferable.
活性エネルギー線の照射量は、活性エネルギー線の種類に応じて適宜に選ぶことができる。例えば、電子線照射により硬化する場合には、その照射量は１〜１５Ｍｒａｄであることが好ましい。また、紫外線照射により硬化する場合には、５０〜１５００ｍＪ／ｃｍ２であることが好ましい。
硬化する際には、空気、窒素やアルゴン等の不活性ガスの雰囲気下であってもよい。
The irradiation amount of the active energy ray can be appropriately selected according to the type of the active energy ray. For example, when it hardens | cures by electron beam irradiation, it is preferable that the irradiation amount is 1-15 Mrad. Moreover, when hardening by ultraviolet irradiation, it is preferable that it is 50-1500 mJ / cm < 2 >.
When curing, an atmosphere of an inert gas such as air, nitrogen or argon may be used.
３次元加工後の意匠性や機能性の発現が良好となる点で、本発明において硬化塗膜の厚さは、目的とされる用途に応じて適宜決められるが、硬化塗膜の厚さの下限値は好ましくは０．５μｍ以上、より好ましくは１μｍ以上である。また、内部硬化性、３次元加工適性が良好となる点で、上限値は好ましくは２０μｍ以下、より好ましくは１５μｍ以下、更に好ましくは１０μｍ以下である。 In the present invention, the thickness of the cured coating film is appropriately determined according to the intended use in that the expression of design and functionality after three-dimensional processing is good. The lower limit is preferably 0.5 μm or more, more preferably 1 μm or more. In addition, the upper limit is preferably 20 μm or less, more preferably 15 μm or less, and even more preferably 10 μm or less in terms of good internal curability and three-dimensional processability.
＜積層体＞
本発明の硬化性重合体組成物の硬化塗膜を有する積層体とは、硬化性重合体組成物を基材に塗布し、乾燥後、活性エネルギー線で硬化させて得られる基材表面に硬化性重合体組成物の硬化物が積層された積層体を意味する。
本発明の積層体は、硬化性重合体組成物を基材に塗布し、乾燥し、活性エネルギー線で硬化させることによって得られる。
<Laminate>
The laminate having a cured coating film of the curable polymer composition of the present invention is cured on the surface of a substrate obtained by applying the curable polymer composition to a substrate, drying and curing with active energy rays. It means a laminate in which a cured product of the polymerizable polymer composition is laminated.
The laminate of the present invention is obtained by applying a curable polymer composition to a substrate, drying, and curing with active energy rays.
３次元加工後の意匠性や機能性の発現が良好となる点で、本発明において硬化塗膜の厚さは、目的とされる用途に応じて適宜決められるが、硬化塗膜の厚さの下限値は好ましくは０．５μｍ以上、より好ましくは１μｍ以上である。また、内部硬化性、３次元加工適性が良好となる点で、上限値は好ましくは２０μｍ以下、より好ましくは１５μｍ以下、更に好ましくは１０μｍ以下である。 In the present invention, the thickness of the cured coating film is appropriately determined according to the intended use in that the expression of design and functionality after three-dimensional processing is good. The lower limit is preferably 0.5 μm or more, more preferably 1 μm or more. In addition, the upper limit is preferably 20 μm or less, more preferably 15 μm or less, and even more preferably 10 μm or less in terms of good internal curability and three-dimensional processability.
＜硬化塗膜の光沢度＞
防眩性が良好となる点から、本発明の積層体を延伸率１００％に延伸した時の６０°光沢度の延伸前後の変化率は、３０以下であることが好ましく、１５以下であることがより好ましい。
なお、ここで「延伸率１００％」とは延伸前の積層体の長さを積層体の長手方向に２．０倍の長さに延伸した延伸率を意味する。
また、前記６０°光沢度の延伸前後の変化率は、日本電色工業社製グロスメーターＶＧ２０００を用いて、未延伸の積層体と延伸率１００％の積層体の６０°鏡面光沢度（６０°グロス）をそれぞれ測定し、その差分の絶対値として測定を行った。
<Glossiness of cured coating film>
From the viewpoint of good antiglare properties, the rate of change before and after stretching of the 60 ° gloss when the laminate of the present invention is stretched to 100% is preferably 30 or less, and 15 or less. Is more preferable.
In addition, "stretching rate 100%" means here the stretch rate which extended | stretched the length of the laminated body before extending | stretching to 2.0 times the length of the laminated body.
Further, the change rate of the 60 ° gloss before and after stretching was determined by using a gloss meter VG2000 manufactured by Nippon Denshoku Industries Co., Ltd. 60 ° specular gloss (60 ° between the unstretched laminate and the laminate having a stretch rate of 100%. Gross) was measured, and the absolute value of the difference was measured.
＜硬化塗膜の延伸率＞
硬化塗膜の延伸性が良好となる点から、本発明の硬化性重合体組成物の硬化塗膜を有する積層体の表面の硬化塗膜がクラックを生じる延伸率は、５０％以上が好ましく、１００％以上がより好ましい。
<Stretch rate of cured coating film>
From the point that the stretchability of the cured coating film is good, the stretch ratio at which the cured coating film on the surface of the laminate having the cured coating film of the curable polymer composition of the present invention has a crack is preferably 50% or more, 100% or more is more preferable.
以下、本発明を実施例及び比較例によりさらに詳しく説明するが、本発明はこれらに限定されるものではない。以下の記載において「部」は質量部を意味する。なお、評価は以下の方法によって行った。 EXAMPLES Hereinafter, although an Example and a comparative example demonstrate this invention further in detail, this invention is not limited to these. In the following description, “parts” means parts by mass. The evaluation was performed by the following method.
＜評価方法＞
以下の実施例及び比較例で調製した塗液（硬化性重合体組成物）を塗布、乾燥し、活性エネルギー線で硬化させることで製造した硬化性重合体組成物の硬化塗膜は、以下の方法により各物性を評価した。
＜評価サンプル＞
実施例で得られた硬化性重合体組成物の塗布液を、厚み１００μｍの易成形ＰＥＴフィルム（帝人デュポン（株）製、ＦＴ７−１００）に＃２０のバーコーターで塗布し、得られた塗膜を７０℃に加熱した熱風乾燥機で６０秒間乾燥を行うことで溶剤を揮発させた。次いで、東芝ライテック社製のＵＶコンベアを用いて、高圧水銀灯により空気下で塗膜の硬化を行ったものを評価サンプルとした。
<Evaluation method>
The coating film (curable polymer composition) prepared in the following examples and comparative examples is coated, dried, and cured with active energy rays. Each physical property was evaluated by the method.
<Evaluation sample>
The coating liquid obtained by applying the coating solution of the curable polymer composition obtained in the example to a 100 μm-thick easily-formed PET film (FT7-100, manufactured by Teijin DuPont Co., Ltd.) with a # 20 bar coater. The solvent was volatilized by drying for 60 seconds with a hot air dryer heated to 70 ° C. Next, an evaluation sample was prepared by curing the coating film in the air with a high-pressure mercury lamp using a UV conveyor manufactured by Toshiba Lighting & Technology.
＜全光線透過率・ヘイズ＞
本発明の積層体の全光線透過率・及びヘイズは、ＪＩＳ Ｚ８７２２Z（透過物体の照射及び受光の幾何条件）及びＪＩＳ Ｋ７３６１−１（プラスチック−透明材料の全光線透過率の試験方法）ＪＩＳ Ｋ７１３６（プラスチック−透明材料のヘ−ズの求め方）に準拠し、日本電色工業製ＳＨ７０００を用いて波長５５０ｎｍにおける値を測定した。
<Total light transmittance / haze>
The total light transmittance and haze of the laminate of the present invention were measured according to JIS Z8722Z (geometric conditions for irradiation and light reception of a transmissive object) and JIS K7361-1 (test method for total light transmittance of plastic-transparent material) JIS K7136 ( The value at a wavelength of 550 nm was measured using SH7000 manufactured by Nippon Denshoku Industries Co., Ltd.
＜光沢度＞
本発明の積層体の光沢度(グロス)は、ＪＩＳ Ｚ ８７４１に準拠し、日本電色工業社製グロスメーターＶＧ２０００を用いて、６０°鏡面光沢度（６０°グロス）として測定を行った。
<Glossiness>
The glossiness (gloss) of the laminate of the present invention was measured as 60 ° specular glossiness (60 ° gloss) using a gloss meter VG2000 manufactured by Nippon Denshoku Industries Co., Ltd. according to JIS Z 8741.
＜防眩性＞
本発明の積層体を、積層体の高さ２．５ｍから蛍光灯を灯し、目視外観にて防眩性（蛍光灯の映り込み）を評価した。
３点：積層体の表面の蛍光灯の反射像は、強くぼやけており、蛍光灯の輪郭が確認できない。
２点：積層体の表面の蛍光灯の反射像は、ぼやけているが、うっすらと輪郭を確認することができる。
１点：積層体の表面の蛍光灯の反射像から、蛍光灯の輪郭を確認することができる。
<Anti-glare property>
The laminate of the present invention was lit with a fluorescent lamp from a height of 2.5 m of the laminate, and the antiglare property (reflection of the fluorescent lamp) was evaluated by visual appearance.
3 points: The reflection image of the fluorescent lamp on the surface of the laminated body is strongly blurred and the outline of the fluorescent lamp cannot be confirmed.
Two points: Although the reflected image of the fluorescent lamp on the surface of the laminate is blurred, the outline can be confirmed slightly.
1 point: The outline of the fluorescent lamp can be confirmed from the reflected image of the fluorescent lamp on the surface of the laminate.
＜延伸率＞
本発明の積層体を１０ｍｍ幅に切断し、引張荷重測定機（（株）イマダ製「ＭＸ２−５００Ｎ」）を用いて、温度１４０℃、引張速度４０ｍｍ／分、チャック間距離４０ｍｍの条件で延伸して破断伸度（目視にてクラックが観察されるまでの伸度）を測定し、以下の基準で評価した。
３点：延伸率１００％以上。
２点：延伸率５０％以上１００％未満。
１点：延伸率５０％未満。
<Stretch rate>
The laminate of the present invention is cut to a width of 10 mm, and stretched using a tensile load measuring device (“MX2-500N” manufactured by Imada Co., Ltd.) at a temperature of 140 ° C., a tensile speed of 40 mm / min, and a distance between chucks of 40 mm. Then, the breaking elongation (elongation until a crack is visually observed) was measured and evaluated according to the following criteria.
3 points: stretch rate of 100% or more.
2 points: Stretching rate of 50% or more and less than 100%.
1 point: Drawing ratio is less than 50%.
＜延伸前後の６０°光沢度変化＞
本発明の積層体を１０ｍｍ幅に切断し、引張荷重測定機（（株）イマダ製「ＭＸ２−５００Ｎ」）を用いて、温度１４０℃、引張速度４０ｍｍ／分、チャック間距離４０ｍｍの条件で１００％に延伸した後の積層体の６０°グロス値（ＧＡ）と、延伸前の積層体の６０°グロス値（ＧＢ）を測定した。ＧＢとＧＡとの差（ΔＧＥ（ΔＧＥ＝ＧＢ−ＧＡの絶対値））を求めて、以下の基準で評価した。
３点：ΔＧＥ≦１５．０
２点：１５．０＜ΔＧＥ≦３０．０
１点：３０．０＜ΔＧＥ
<60 ° gloss change before and after stretching>
The laminate of the present invention is cut to a width of 10 mm, and a tensile load measuring device (“MX2-500N” manufactured by Imada Co., Ltd.) is used to measure 100 at a temperature of 140 ° C., a tensile speed of 40 mm / min, and a chuck distance of 40 mm. The 60 ° gloss value (GA) of the laminate after stretching to% and the 60 ° gloss value (GB) of the laminate before stretching were measured. A difference between GB and GA (ΔGE (ΔGE = absolute value of GB−GA)) was determined and evaluated according to the following criteria.
3 points: ΔGE ≦ 15.0
2 points: 15.0 <ΔGE ≦ 30.0
1 point: 30.0 <ΔGE
＜ギラツキ性＞
本発明の積層体を緑色の画像を表示させたアップル社製ｉＰａｄ（ＭＤ５１３ＫＨ/Ａ)シリーズ上に貼り合わせ、真上より目視にて樹脂フィルムのギラツキを評価した。
２点：ギラツキに伴う色ムラが見られず、良好なディスプレイの視認性を維持する。
１点：ギラツキに伴う色ムラが見られ、僅かにディスプレイの視認性が低下する。
<Glittering>
The laminate of the present invention was bonded onto an Apple iPad (MD513KH / A) series displaying a green image, and the glare of the resin film was evaluated visually from directly above.
2 points: Color unevenness due to glare is not seen, and good display visibility is maintained.
1 point: Color unevenness due to glare is seen, and the visibility of the display slightly decreases.
＜耐擦傷性＞
本発明の積層体について、耐擦傷試験前に測定した６０°グロス値をＧ１とした。一方、２３℃、５５％ＲＨの雰囲気下、ボンスター製スチールウール（＃００００）に２００ｇの錘（面積１．７０ｃｍ２）を載せ、硬化塗膜面を学振磨耗試験機（東洋精機製）で１０往復擦り、直後に測定した６０°グロス値をＧ２とした。Ｇ２とＧ１との差（ΔＧＴ（ΔＧ＝Ｇ２−Ｇ１の絶対値））を求めて、以下の基準で評価した。
３点：６．０＜ΔＧＴ≦９．９
２点：１０．０＜ΔＧＴ≦１９．９
１点：２０．０＜ΔＧＴ
<Abrasion resistance>
About the laminated body of this invention, the 60 degree gloss value measured before the abrasion-resistance test was set to G1. On the other hand, in an atmosphere of 23 ° C. and 55% RH, a 200 g weight (area: 1.70 cm 2 ) is placed on Bonster steel wool (# 0000), and the cured coating surface is subjected to a Gakusei Abrasion Tester (manufactured by Toyo Seiki). Rub 10 reciprocations, and the 60 ° gloss value measured immediately after that was G2. The difference (ΔGT (ΔG = the absolute value of G2−G1)) between G2 and G1 was determined and evaluated according to the following criteria.
3 points: 6.0 <ΔGT ≦ 9.9
2 points: 10.0 <ΔGT ≦ 19.9
1 point: 20.0 <ΔGT
＜製造例１：不飽和二重結合を含む重合体Ａ−１の合成＞
温度計、攪拌機及び還流冷却管を備えたフラスコに、プロピレングリコールモノメチルエーテル３７６．４部、グリシジルメタクリレート４０．０部、メチルメタクリレート１５８．０部、エチルアクリレート２．０部、及び２，２’−アゾビス（２，４−ジメチルバレロニトリル）１．２部を入れ、６５℃で３時間反応させた。
その後、更に２，２’−アゾビス（２，４−ジメチルバレロニトリル）０．６部を加え３時間反応させた後、プロピレングリコールモノメチルエーテル４３．６部、ｐ−メトキシフェノール１．０部を加え１００℃まで加熱した。
次に、アクリル酸２０．７部、及びトリフェニルホスフィン２．６５部を添加して、１１０℃で６時間反応させることで、固形分３５％の重合体Ａ−１得た。
重合体Ａ−１のアクリロイル当量（アクリロイル基の導入量）は１．２４ｍｍｏｌ／ｇ、２級水酸基は１．２４ｍｍｏｌ／ｇ含む（メタ）であり、また、ガラス転移温度は８４℃、ＳＰ値は１５．０、重量平均分子量は４８,８００であった。
<Production Example 1: Synthesis of polymer A-1 containing unsaturated double bond>
In a flask equipped with a thermometer, stirrer and reflux condenser, 376.4 parts propylene glycol monomethyl ether, 40.0 parts glycidyl methacrylate, 158.0 parts methyl methacrylate, 2.0 parts ethyl acrylate, and 2,2′- 1.2 parts of azobis (2,4-dimethylvaleronitrile) was added and reacted at 65 ° C. for 3 hours.
Thereafter, 0.6 parts of 2,2′-azobis (2,4-dimethylvaleronitrile) was further added and reacted for 3 hours, and then 43.6 parts of propylene glycol monomethyl ether and 1.0 part of p-methoxyphenol were added. Heated to 100 ° C.
Next, 20.7 parts of acrylic acid and 2.65 parts of triphenylphosphine were added and reacted at 110 ° C. for 6 hours to obtain a polymer A-1 having a solid content of 35%.
Polymer A-1 has an acryloyl equivalent (introduction amount of acryloyl group) of 1.24 mmol / g, a secondary hydroxyl group containing 1.24 mmol / g (meth), a glass transition temperature of 84 ° C., and an SP value of The weight average molecular weight was 15.0 and the weight average molecular weight was 48,800.
＜製造例２：不飽和二重結合を含む重合体Ａ−２の合成＞
温度計、攪拌機及び還流冷却管を備えたフラスコに、プロピレングリコールモノメチルエーテル５１７．６部、グリシジルメタクリレート１１０．０部、メチルメタクリレート１６２．３部、エチルアクリレート２．８部、及び２，２’−アゾビス（２，４−ジメチルバレロニトリル）１．７部を入れ、６５℃で３時間反応させた。
その後、更に２，２’−アゾビス（２，４−ジメチルバレロニトリル）０．８部を加え３時間反応させた後、プロピレングリコールモノメチルエーテル１０１．０部、ｐ−メトキシフェノール１．４部を加え１００℃まで加熱した。
次に、アクリル酸５６．８部、及びトリフェニルホスフィン４．０部を添加して、１１０℃で６時間反応させることで、固形分３５％の重合体Ａ−２を得た。
重合体Ａ−２のアクリロイル当量（アクリロイル基の導入量）は２．２７ｍｍｏｌ／ｇ、２級水酸基は２．２７ｍｍｏｌ／ｇ含む（メタ）であり、また、ガラス転移温度は５５℃、ＳＰ値は１５．８、重量平均分子量は５０,０００であった。
<Production Example 2: Synthesis of polymer A-2 containing unsaturated double bond>
In a flask equipped with a thermometer, stirrer and reflux condenser, 517.6 parts propylene glycol monomethyl ether, 110.0 parts glycidyl methacrylate, 162.3 parts methyl methacrylate, 2.8 parts ethyl acrylate, and 2,2′- 1.7 parts of azobis (2,4-dimethylvaleronitrile) was added and reacted at 65 ° C. for 3 hours.
Thereafter, 0.8 parts of 2,2′-azobis (2,4-dimethylvaleronitrile) was further added and reacted for 3 hours, and then 101.0 parts of propylene glycol monomethyl ether and 1.4 parts of p-methoxyphenol were added. Heated to 100 ° C.
Next, 56.8 parts of acrylic acid and 4.0 parts of triphenylphosphine were added and reacted at 110 ° C. for 6 hours to obtain a polymer A-2 having a solid content of 35%.
Polymer A-2 has an acryloyl equivalent (amount of acryloyl group introduced) of 2.27 mmol / g, a secondary hydroxyl group of 2.27 mmol / g (meta), a glass transition temperature of 55 ° C., and an SP value of The weight average molecular weight was 150,000 and the weight average molecular weight was 50,000.
＜製造例３：不飽和二重結合を含む重合体Ａ−３の合成＞
温度計、攪拌機及び還流冷却管を備えたフラスコに、プロピレングリコールモノメチルエーテル３０４．１部、グリシジルメタクリレート１９６．０部、メチルメタクリレート２．０部、エチルアクリレート２．０部、メルカプトプロピルトリメトキシシラン３．８部、及び２，２’−アゾビス（２，４−ジメチルバレロニトリル）２．０部を入れ、６５℃で３時間反応させた。
その後、更に２，２’−アゾビス（２，４−ジメチルバレロニトリル）１．０部を加え３時間反応させた後、プロピレングリコールモノメチルエーテル２７１．９部、ｐ−メトキシフェノール０．９部を加え１００℃まで加熱した。
次に、アクリル酸１０１．４部、及びトリフェニルホスフィン３．６６部を添加して、１１０℃で６時間反応させることで、固形分３５％の重合体Ａ−２得た。
重合体Ａ−３のアクリロイル当量（アクリロイル基の導入量）は４．４７ｍｍｏｌ／ｇ、２級水酸基は４．４７ｍｍｏｌ／ｇ含む（メタ）であり、また、ガラス転移温度は３２℃、ＳＰ値は１７．４、重量平均分子量は１８,８００であった。
<Production Example 3: Synthesis of polymer A-3 containing an unsaturated double bond>
In a flask equipped with a thermometer, stirrer and reflux condenser, 304.1 parts propylene glycol monomethyl ether, 196.0 parts glycidyl methacrylate, 2.0 parts methyl methacrylate, 2.0 parts ethyl acrylate, mercaptopropyltrimethoxysilane 3 8 parts and 2.0 parts of 2,2′-azobis (2,4-dimethylvaleronitrile) were added and reacted at 65 ° C. for 3 hours.
Thereafter, 1.0 part of 2,2′-azobis (2,4-dimethylvaleronitrile) was further added and reacted for 3 hours, and then 271.9 parts of propylene glycol monomethyl ether and 0.9 part of p-methoxyphenol were added. Heated to 100 ° C.
Next, 101.4 parts of acrylic acid and 3.66 parts of triphenylphosphine were added and reacted at 110 ° C. for 6 hours to obtain a polymer A-2 having a solid content of 35%.
Polymer A-3 has an acryloyl equivalent (amount of acryloyl group introduced) of 4.47 mmol / g, secondary hydroxyl group containing 4.47 mmol / g (meth), a glass transition temperature of 32 ° C., and an SP value of 17.4 and the weight average molecular weight were 18,800.
＜製造例４：分散剤の製造＞
撹拌機、冷却管、温度計を備えた重合装置中に、脱イオン水９００部、メタクリル酸２−スルホエチルナトリウム６０部、メタクリル酸カリウム１０部及びメチルメタクリレート１２部を入れて撹拌し、重合装置内を窒素置換しながら、５０℃に昇温した。その中に、重合開始剤として２，２’−アゾビス（２−メチルプロピオンアミジン）二塩酸塩０．０８部を添加し、更に６０℃に昇温した。昇温後、滴下ポンプを使用して、メチルメタクリレートを０．２４部／分の速度で７５分間連続的に滴下した。滴下終了後、反応溶液を６０℃で６時間保持した後、室温に冷却して、透明な水溶液である固形分１０％の分散剤を得た。
<Production Example 4: Production of dispersant>
In a polymerization apparatus equipped with a stirrer, a condenser, and a thermometer, 900 parts of deionized water, 60 parts of sodium 2-sulfoethyl methacrylate, 10 parts of potassium methacrylate and 12 parts of methyl methacrylate were stirred and polymerized. While the inside was replaced with nitrogen, the temperature was raised to 50 ° C. In this, 0.08 part of 2,2′-azobis (2-methylpropionamidine) dihydrochloride was added as a polymerization initiator, and the temperature was further raised to 60 ° C. After the temperature elevation, methyl methacrylate was continuously added dropwise at a rate of 0.24 parts / minute for 75 minutes using a dropping pump. After completion of the dropwise addition, the reaction solution was kept at 60 ° C. for 6 hours and then cooled to room temperature to obtain a dispersant having a solid content of 10% as a transparent aqueous solution.
＜製造例５：重合体Ｂ−１の合成＞
撹拌機、冷却管、温度計を備えた重合装置中に、脱イオン水１４５部、硫酸ナトリウム０．１部及び分散剤（固形分１０％）０．２５部を入れて撹拌し、均一な水溶液とした。次に、スチレン７５部、メチルメタアクリレート２５部、２，２’−アゾビス（２−メチルブチロニトリル）１．５部を加え水性懸濁液とした。
次に、重合装置内を窒素置換し、７５℃に昇温して１時間反応し、更に重合率を上げるため、後処理温度として９８℃に昇温して３０分保持した。その後、反応液を４０℃に冷却して、ポリマーを含む水性懸濁液を得た。この水性懸濁液を目開き４５μｍのナイロン製濾過布で濾過し、濾過物を脱イオン水で洗浄し、脱水し、５０℃で１６時間乾燥して、重合体Ａに非相溶性の重合体Ｂ−１を得た。
重合体Ｂ−１のガラス転移温度は９３℃、ＳＰ値は１０．２、重量平均分子量は６４,３００であった。
<Production Example 5: Synthesis of polymer B-1>
In a polymerization apparatus equipped with a stirrer, a condenser, and a thermometer, 145 parts of deionized water, 0.1 part of sodium sulfate, and 0.25 part of a dispersant (solid content 10%) were added and stirred to obtain a uniform aqueous solution. It was. Next, 75 parts of styrene, 25 parts of methyl methacrylate and 1.5 parts of 2,2′-azobis (2-methylbutyronitrile) were added to obtain an aqueous suspension.
Next, the inside of the polymerization apparatus was purged with nitrogen, heated to 75 ° C., reacted for 1 hour, and further heated to 98 ° C. as a post-treatment temperature and held for 30 minutes in order to increase the polymerization rate. Thereafter, the reaction solution was cooled to 40 ° C. to obtain an aqueous suspension containing the polymer. The aqueous suspension is filtered through a nylon filter cloth having a mesh opening of 45 μm, and the filtrate is washed with deionized water, dehydrated, and dried at 50 ° C. for 16 hours to obtain a polymer incompatible with polymer A. B-1 was obtained.
Polymer B-1 had a glass transition temperature of 93 ° C., an SP value of 10.2, and a weight average molecular weight of 64,300.
＜製造例６：重合体Ｂ−２の合成＞
撹拌機、冷却管、温度計を備えた重合装置中に、脱イオン水１４５部、硫酸ナトリウム０．１部及び分散剤（固形分１０％）０．２５部を入れて撹拌し、均一な水溶液とした。次に、メチルメタクリレート１００部、オクチルメルカプタン０．２部、２，２’−アゾビス（２−メチルブチロニトリル）０．１部を加え水性懸濁液とした。
次に、重合装置内を窒素置換し、７５℃に昇温して１時間反応し、更に重合率を上げるため、後処理温度として９８℃に昇温して３０分保持した。その後、反応液を４０℃に冷却して、ポリマーを含む水性懸濁液を得た。この水性懸濁液を目開き４５μｍのナイロン製濾過布で濾過し、濾過物を脱イオン水で洗浄し、脱水し、５０℃で１６時間乾燥して、ア重合体Ａに非相溶性の重合体Ｂ−２を得た。
重合体Ｂ−２のガラス転移温度は１０４℃、ＳＰ値は１３．４、重量平均分子量は９７,３００であった。
<Production Example 6: Synthesis of polymer B-2>
In a polymerization apparatus equipped with a stirrer, a condenser, and a thermometer, 145 parts of deionized water, 0.1 part of sodium sulfate, and 0.25 part of a dispersant (solid content 10%) were added and stirred to obtain a uniform aqueous solution. It was. Next, 100 parts of methyl methacrylate, 0.2 part of octyl mercaptan, and 0.1 part of 2,2′-azobis (2-methylbutyronitrile) were added to obtain an aqueous suspension.
Next, the inside of the polymerization apparatus was purged with nitrogen, heated to 75 ° C., reacted for 1 hour, and further heated to 98 ° C. as a post-treatment temperature and held for 30 minutes in order to increase the polymerization rate. Thereafter, the reaction solution was cooled to 40 ° C. to obtain an aqueous suspension containing the polymer. This aqueous suspension is filtered through a nylon filter cloth having a mesh opening of 45 μm, and the filtrate is washed with deionized water, dehydrated, dried at 50 ° C. for 16 hours, and is incompatible with polymer A. Combined B-2 was obtained.
Polymer B-2 had a glass transition temperature of 104 ° C., an SP value of 13.4, and a weight average molecular weight of 97,300.
本発明の硬化性重合体組成物で使用した重合体Ａ、重合体Ｂ及び多官能（メタ）アクリレートＣのＳＰ値、二重結合量、及び重合体Ａ、重合体Ｂのガラス転移温度を表１に示す。 The SP value of the polymer A, the polymer B and the polyfunctional (meth) acrylate C used in the curable polymer composition of the present invention, the double bond amount, and the glass transition temperature of the polymer A and the polymer B are shown. It is shown in 1.
＜実施例１＞
撹拌子を備えたフラスコ中に、重合体ＡとしてＡ−１を樹脂固形分で７５部、重合体ＢとしてＢ−１を樹脂固形分で２５部、光開始剤として１−ヒドロキシ−シクロヘキシル−フェニル−ケトン（ＩＧＭ Ｒｅｓｉｎｓ社製 Ｏｍｎｉｒａｄ １８４）を３部加えた。この混合物に対して、重合体Ｂに対して不溶性である溶剤としてプロピレングリコールモノメチルエーテル、重合体Ａ及びＢに対して良溶媒であるメチルエチルケトンの重量比１対１の混合溶剤を添加し、固形分１３．０％の塗布液となるよう調製した。
この塗布液を、厚み１００μｍの易成形ＰＥＴフィルム（帝人デュポン（株）製、ＦＴ７−１００）に＃２０のバーコーターで塗布し、７０℃に加熱した熱風乾燥機で６０秒間乾燥を行うことで溶剤を揮発させた。次いで、東芝ライテック社製のＵＶコンベアを用いて、高圧水銀灯により空気下で塗膜の硬化を行った。光硬化は、波長３００〜３９０ｎｍの積算光量が、岩崎電気株式会社製の照度計（アイ紫外線積算照度計 ＵＶＰＦ―Ａ１、ＰＤ−３６５）で測定した際に、３００ｍＪ／ｃｍ２（２５０ｍＷ/Ｊ／ｃｍ２）となるように調整し、1回の露光を行った。
<Example 1>
In a flask equipped with a stir bar, A-1 as polymer A is 75 parts in resin solid content, B-1 as polymer B is 25 parts in resin solid content, and 1-hydroxy-cyclohexyl-phenyl as photoinitiator. -3 parts of a ketone (Omnirad 184 from IGM Resins) was added. To this mixture was added propylene glycol monomethyl ether as a solvent insoluble in polymer B, and a mixed solvent of methyl ethyl ketone, which is a good solvent for polymers A and B, in a weight ratio of 1: 1, It was prepared to be a 13.0% coating solution.
This coating solution is applied to an easily molded PET film having a thickness of 100 μm (FT7-100, manufactured by Teijin DuPont Co., Ltd.) with a # 20 bar coater and dried for 60 seconds with a hot air dryer heated to 70 ° C. The solvent was volatilized. Subsequently, the coating film was cured under air with a high-pressure mercury lamp using a UV conveyor manufactured by Toshiba Lighting & Technology. In photocuring, when the accumulated light amount of a wavelength of 300 to 390 nm is measured by an illuminance meter (eye ultraviolet ray illuminance meter UVPF-A1, PD-365) manufactured by Iwasaki Electric Co., Ltd., 300 mJ / cm 2 (250 mW / J / cm 2 ), and exposure was performed once.
＜実施例２〜６及び比較例１＞
硬化性重合体組成物の組成を表２に示す配合に変更した以外は、実施例１と同様に活性エネルギー線重合性組成物を調製し、これを用いて硬化塗膜付の樹脂積層体を作製し、評価を行った。実施例１〜６及び比較例１の評価結果を表２に示す
<Examples 2 to 6 and Comparative Example 1>
An active energy ray polymerizable composition was prepared in the same manner as in Example 1 except that the composition of the curable polymer composition was changed to the formulation shown in Table 2, and a resin laminate with a cured coating film was prepared using the active energy ray polymerizable composition. Fabricated and evaluated. The evaluation results of Examples 1 to 6 and Comparative Example 1 are shown in Table 2.
表２からもわかるように、二重結合当量が４ｍｍｏｌ／ｇよりも大きい比較例１は延伸性が低く、総合評価点が低かった。 As can be seen from Table 2, Comparative Example 1 having a double bond equivalent greater than 4 mmol / g has low stretchability and a low overall evaluation score.
Claims (9)
（１）ＳＰＡ−ＳＰＢ≧０．５
（２）重合体Ａが不飽和二重結合を有し、二重結合当量が０．１ｍｍｏｌ／ｇ以上４ｍｍｏｌ／ｇ以下
（ＳＰＡ、ＳＰＢはそれぞれ、前記重合体Ａ、前記重合体Ｂの溶解度パラメータを示す。） A polymer A, a curable polymer composition having a solubility parameter (SP value) different from that of the polymer A and containing an incompatible polymer B and a polyfunctional (meth) acrylate C in the polymer A, A curable polymer composition satisfying (1) and (2).
(1) SPA-SPB ≧ 0.5
(2) Polymer A has an unsaturated double bond, and the double bond equivalent is 0.1 mmol / g or more and 4 mmol / g or less (SPA and SPB are the solubility parameters of Polymer A and Polymer B, respectively) Is shown.)
（３）ＳＰＣ−ＳＰＢ≦(ＳＰＡ−ＳＰＣ)×２．５
（ＳＰＣは前記多官能（メタ）アクリレートＣの溶解度パラメータを示す。） The curable polymer composition of Claim 1 which satisfies the following (3).
(3) SPC-SPB ≦ (SPA-SPC) × 2.5
(SPC indicates the solubility parameter of the polyfunctional (meth) acrylate C)
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| JP2022025617A (en) * | 2020-07-29 | 2022-02-10 | 三菱ケミカル株式会社 | Cured film and laminate, and method for producing the same |
| JP2022025624A (en) * | 2020-07-29 | 2022-02-10 | 三菱ケミカル株式会社 | Cured film and laminate, and method for producing the same |
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| JP2022025624A (en) * | 2020-07-29 | 2022-02-10 | 三菱ケミカル株式会社 | Cured film and laminate, and method for producing the same |
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