JPWO2016203957A1 - 硬化性組成物、及び成形体 - Google Patents
硬化性組成物、及び成形体 Download PDFInfo
- Publication number
- JPWO2016203957A1 JPWO2016203957A1 JP2017524799A JP2017524799A JPWO2016203957A1 JP WO2016203957 A1 JPWO2016203957 A1 JP WO2016203957A1 JP 2017524799 A JP2017524799 A JP 2017524799A JP 2017524799 A JP2017524799 A JP 2017524799A JP WO2016203957 A1 JPWO2016203957 A1 JP WO2016203957A1
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- Prior art keywords
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- silicone resin
- curable composition
- formula
- present
- Prior art date
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- 229960001755 resorcinol Drugs 0.000 description 1
- 239000006254 rheological additive Substances 0.000 description 1
- 238000007151 ring opening polymerisation reaction Methods 0.000 description 1
- 238000007788 roughening Methods 0.000 description 1
- 125000002914 sec-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 description 1
- 229910010271 silicon carbide Inorganic materials 0.000 description 1
- HQVNEWCFYHHQES-UHFFFAOYSA-N silicon nitride Chemical compound N12[Si]34N5[Si]62N3[Si]51N64 HQVNEWCFYHHQES-UHFFFAOYSA-N 0.000 description 1
- 125000005373 siloxane group Chemical group [SiH2](O*)* 0.000 description 1
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- 239000004332 silver Substances 0.000 description 1
- 239000001632 sodium acetate Substances 0.000 description 1
- 235000017281 sodium acetate Nutrition 0.000 description 1
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 1
- 235000017557 sodium bicarbonate Nutrition 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
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- 239000000600 sorbitol Substances 0.000 description 1
- 239000003549 soybean oil Substances 0.000 description 1
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- 239000007921 spray Substances 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 239000008117 stearic acid Substances 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
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- 229920003048 styrene butadiene rubber Polymers 0.000 description 1
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- 239000005061 synthetic rubber Substances 0.000 description 1
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 150000003512 tertiary amines Chemical class 0.000 description 1
- 125000005497 tetraalkylphosphonium group Chemical group 0.000 description 1
- BJQWBACJIAKDTJ-UHFFFAOYSA-N tetrabutylphosphanium Chemical class CCCC[P+](CCCC)(CCCC)CCCC BJQWBACJIAKDTJ-UHFFFAOYSA-N 0.000 description 1
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- QEMXHQIAXOOASZ-UHFFFAOYSA-N tetramethylammonium Chemical class C[N+](C)(C)C QEMXHQIAXOOASZ-UHFFFAOYSA-N 0.000 description 1
- 125000000383 tetramethylene group Chemical group [H]C([H])([*:1])C([H])([H])C([H])([H])C([H])([H])[*:2] 0.000 description 1
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- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 description 1
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- SEACXNRNJAXIBM-UHFFFAOYSA-N triethyl(methyl)azanium Chemical class CC[N+](C)(CC)CC SEACXNRNJAXIBM-UHFFFAOYSA-N 0.000 description 1
- CZMCQLHUFVDMLM-UHFFFAOYSA-N triethyl(phenacyl)phosphanium Chemical class CC[P+](CC)(CC)CC(=O)C1=CC=CC=C1 CZMCQLHUFVDMLM-UHFFFAOYSA-N 0.000 description 1
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- ZNOCGWVLWPVKAO-UHFFFAOYSA-N trimethoxy(phenyl)silane Chemical compound CO[Si](OC)(OC)C1=CC=CC=C1 ZNOCGWVLWPVKAO-UHFFFAOYSA-N 0.000 description 1
- DQZNLOXENNXVAD-UHFFFAOYSA-N trimethoxy-[2-(7-oxabicyclo[4.1.0]heptan-4-yl)ethyl]silane Chemical compound C1C(CC[Si](OC)(OC)OC)CCC2OC21 DQZNLOXENNXVAD-UHFFFAOYSA-N 0.000 description 1
- QXJQHYBHAIHNGG-UHFFFAOYSA-N trimethylolethane Chemical compound OCC(C)(CO)CO QXJQHYBHAIHNGG-UHFFFAOYSA-N 0.000 description 1
- MGACORKJUSACCA-UHFFFAOYSA-N trinaphthalen-1-ylsulfanium Chemical class C1=CC=C2C([S+](C=3C4=CC=CC=C4C=CC=3)C=3C4=CC=CC=C4C=CC=3)=CC=CC2=C1 MGACORKJUSACCA-UHFFFAOYSA-N 0.000 description 1
- HKDYXDHJQBAOAC-UHFFFAOYSA-N trinaphthalen-2-ylsulfanium Chemical class C1=CC=CC2=CC([S+](C=3C=C4C=CC=CC4=CC=3)C3=CC4=CC=CC=C4C=C3)=CC=C21 HKDYXDHJQBAOAC-UHFFFAOYSA-N 0.000 description 1
- WLOQLWBIJZDHET-UHFFFAOYSA-N triphenylsulfonium Chemical class C1=CC=CC=C1[S+](C=1C=CC=CC=1)C1=CC=CC=C1 WLOQLWBIJZDHET-UHFFFAOYSA-N 0.000 description 1
- AXYQQAVHPAUFQX-UHFFFAOYSA-N tris(2-methylphenyl)sulfanium Chemical class CC1=CC=CC=C1[S+](C=1C(=CC=CC=1)C)C1=CC=CC=C1C AXYQQAVHPAUFQX-UHFFFAOYSA-N 0.000 description 1
- MAOCPIDAEMTJLK-UHFFFAOYSA-N tris(4-fluorophenyl)sulfanium Chemical class C1=CC(F)=CC=C1[S+](C=1C=CC(F)=CC=1)C1=CC=C(F)C=C1 MAOCPIDAEMTJLK-UHFFFAOYSA-N 0.000 description 1
- XUWXFPUSCUUNPR-UHFFFAOYSA-O tris(4-hydroxyphenyl)sulfanium Chemical class C1=CC(O)=CC=C1[S+](C=1C=CC(O)=CC=1)C1=CC=C(O)C=C1 XUWXFPUSCUUNPR-UHFFFAOYSA-O 0.000 description 1
- WUKMCKCDYKBLBG-UHFFFAOYSA-N tris(4-methoxyphenyl)sulfanium Chemical class C1=CC(OC)=CC=C1[S+](C=1C=CC(OC)=CC=1)C1=CC=C(OC)C=C1 WUKMCKCDYKBLBG-UHFFFAOYSA-N 0.000 description 1
- QKFJVDSYTSWPII-UHFFFAOYSA-N tris(4-methylphenyl)sulfanium Chemical class C1=CC(C)=CC=C1[S+](C=1C=CC(C)=CC=1)C1=CC=C(C)C=C1 QKFJVDSYTSWPII-UHFFFAOYSA-N 0.000 description 1
- 239000006097 ultraviolet radiation absorber Substances 0.000 description 1
- JABYJIQOLGWMQW-UHFFFAOYSA-N undec-4-ene Chemical compound CCCCCCC=CCCC JABYJIQOLGWMQW-UHFFFAOYSA-N 0.000 description 1
- 229920006163 vinyl copolymer Polymers 0.000 description 1
- 229920001959 vinylidene polymer Polymers 0.000 description 1
- 239000004034 viscosity adjusting agent Substances 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- 239000001993 wax Substances 0.000 description 1
- 238000004018 waxing Methods 0.000 description 1
- 210000002268 wool Anatomy 0.000 description 1
- 229910052724 xenon Inorganic materials 0.000 description 1
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
- 125000002256 xylenyl group Chemical class C1(C(C=CC=C1)C)(C)* 0.000 description 1
- 125000006839 xylylene group Chemical group 0.000 description 1
- 239000011787 zinc oxide Substances 0.000 description 1
- INRGAWUQFOBNKL-UHFFFAOYSA-N {4-[(Vinyloxy)methyl]cyclohexyl}methanol Chemical compound OCC1CCC(COC=C)CC1 INRGAWUQFOBNKL-UHFFFAOYSA-N 0.000 description 1
- PAPBSGBWRJIAAV-UHFFFAOYSA-N ε-Caprolactone Chemical compound O=C1CCCCCO1 PAPBSGBWRJIAAV-UHFFFAOYSA-N 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D183/00—Coating compositions based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon, with or without sulfur, nitrogen, oxygen, or carbon only; Coating compositions based on derivatives of such polymers
- C09D183/04—Polysiloxanes
- C09D183/06—Polysiloxanes containing silicon bound to oxygen-containing groups
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- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
- C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
- C08G59/40—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the curing agents used
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
- C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
- C08G59/40—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the curing agents used
- C08G59/4007—Curing agents not provided for by the groups C08G59/42 - C08G59/66
- C08G59/4085—Curing agents not provided for by the groups C08G59/42 - C08G59/66 silicon containing compounds
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
- C08G77/04—Polysiloxanes
- C08G77/14—Polysiloxanes containing silicon bound to oxygen-containing groups
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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- C08G77/14—Polysiloxanes containing silicon bound to oxygen-containing groups
- C08G77/18—Polysiloxanes containing silicon bound to oxygen-containing groups to alkoxy or aryloxy groups
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- C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
- C08G77/04—Polysiloxanes
- C08G77/38—Polysiloxanes modified by chemical after-treatment
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- C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
- C08J7/04—Coating
- C08J7/0427—Coating with only one layer of a composition containing a polymer binder
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- C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
- C08J7/04—Coating
- C08J7/043—Improving the adhesiveness of the coatings per se, e.g. forming primers
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- C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
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- C08J7/046—Forming abrasion-resistant coatings; Forming surface-hardening coatings
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- C08L33/04—Homopolymers or copolymers of esters
- C08L33/14—Homopolymers or copolymers of esters of esters containing halogen, nitrogen, sulfur, or oxygen atoms in addition to the carboxy oxygen
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- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
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- C08J2433/04—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers esters
- C08J2433/14—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers esters of esters containing halogen, nitrogen, sulfur, or oxygen atoms in addition to the carboxy oxygen
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Abstract
Description
また、本発明の他の目的は、高い表面硬度を維持しながら、可とう性を有し、ロールトゥロール方式での製造や加工が可能なハードコート層を有する成形体を提供することにある。
で表される構成単位の割合が50モル%以上である前記の硬化性組成物を提供する。
で表される構成単位を含み、式(I)で表される構成単位と式(II)で表される構成単位のモル比[式(I)で表される構成単位/式(II)で表される構成単位]が5以上である前記の硬化性組成物を提供する。
で表される構成単位、及び下記式(2)
で表される構成単位を含む前記の硬化性組成物を提供する。
[1]カチオン硬化性シリコーン樹脂、前記カチオン硬化性シリコーン樹脂以外のエポキシ化合物、及びレベリング剤を含有し、前記カチオン硬化性シリコーン樹脂が、シルセスキオキサン単位を含み、前記カチオン硬化性シリコーン樹脂におけるシロキサン構成単位の全量に対するエポキシ基を有する構成単位の割合が50モル%以上であり、数平均分子量が1000〜3000であるシリコーン樹脂であることを特徴とする硬化性組成物。
[2]前記エポキシ化合物が、脂環式エポキシ化合物である[1]に記載の硬化性組成物。
[3]前記エポキシ化合物が、シクロヘキセンオキシド基を有する化合物である[1]又は[2]に記載の硬化性組成物。
[4]カチオン硬化性シリコーン樹脂、水酸基、カルボキシル基、及びエポキシ基からなる群から選択される少なくとも1つの基を有する(メタ)アクリル酸エステル系樹脂、及びレベリング剤を含み、前記カチオン硬化性シリコーン樹脂が、単量体を構成する単位としてシルセスキオキサン単位を含み、全単量体単位のうちエポキシ基を有する単量体単位の割合が、50モル%以上であり、且つ数平均分子量が、1000〜3000である硬化性組成物。
[5]前記(メタ)アクリル酸エステル系樹脂の割合が、前記カチオン硬化性シリコーン樹脂100重量部に対して、0.1〜20重量部である[4]に記載の硬化性組成物。
[6]前記カチオン硬化性シリコーン樹脂におけるシロキサン構成単位の全量に対する、式(I)で表される構成単位の割合が50モル%以上である[1]〜[5]のいずれか1つに記載の硬化性組成物。
[7]前記カチオン硬化性シリコーン樹脂が、さらに、式(II)で表される構成単位を含み、式(I)で表される構成単位と式(II)で表される構成単位のモル比[式(I)で表される構成単位/式(II)で表される構成単位]が5以上である[6]に記載の硬化性組成物。
[8]前記シルセスキオキサン単位として、式(1)で表される構成単位、及び式(2)で表される構成単位を含む[1]〜[7]のいずれか1つに記載の硬化性組成物。
[9]前記カチオン硬化性シリコーン樹脂の分子量分散度(重量平均分子量/数平均分子量)が1.0〜3.0である[1]〜[8]のいずれか1つに記載の硬化性組成物。
[10]前記レベリング剤が、シリコーン系レベリング剤及びフッ素系レベリング剤からなる群より選択される1種以上のレベリング剤であり、かつエポキシ基と反応性を有する基及び加水分解縮合性基からなる群より選択される1種以上の基を有する[1]〜[9]のいずれか1つに記載の硬化性組成物。
[11]前記レベリング剤の含有量(配合量)が、前記カチオン硬化性シリコーン樹脂の全量100重量部に対して、0.001〜20重量部である[1]〜[10]のいずれか1つに記載の硬化性組成物。
[12]前記レベリング剤が、ヒドロキシル基を有するシリコーン系レベリング剤であり、且つレベリング剤の割合が、前記カチオン硬化性シリコーン樹脂100重量部に対して、0.01〜5重量部である[1]〜[11]のいずれか1つに記載の硬化性組成物。
[13]前記式(1)中のR1が、後述の式(1a)〜(1d)で表される基を少なくとも1つ含む[8]〜[12]のいずれか1つに記載の硬化性組成物。
[14]水酸基を有する(メタ)アクリル酸エステル系樹脂の割合が、前記カチオン硬化性シリコーン樹脂100重量部に対して、0.1〜20重量部である[4]〜[13]のいずれか1つに記載の硬化性組成物。
[15]カルボキシル基を有する(メタ)アクリル酸エステル系樹脂の割合が、前記カチオン硬化性シリコーン樹脂100重量部に対して、0.1〜20重量部である[4]〜[13]のいずれか1つに記載の硬化性組成物。
[16]エポキシ基を有する(メタ)アクリル酸エステル系樹脂の割合が、前記カチオン硬化性シリコーン樹脂100重量部に対して、0.1〜20重量部である[4]〜[13]のいずれか1つに記載の硬化性組成物。
[17]さらに、硬化触媒を含む[1]〜[16]のいずれか1つに記載の硬化性組成物。
[18]前記硬化触媒が、光カチオン重合開始剤又は熱カチオン重合開始剤である[17]に記載の硬化性組成物。
[19]ハードコート層形成用硬化性組成物である[1]〜[18]のいずれか1つに記載の硬化性組成物。
[20][1]〜[19]のいずれか1つに記載の硬化性組成物の硬化物。
[21][1]〜[19]のいずれか1つに記載の硬化性組成物の硬化物で形成されたハードコート層を有する成形体。
[22]前記ハードコート層の厚みが、0.1〜200μmである[21]に記載の成形体。
[23]前記ハードコート層の少なくとも一方の面に積層された透明基材層を有する[21]又は[22]に記載の成形体。
[24]ロールトゥロール方式で製造された[21]〜[23]のいずれか1つに記載の成形体。
本発明の硬化性組成物に含まれるカチオン硬化性シリコーン樹脂は、シルセスキオキサン単位を含み、上記カチオン硬化性シリコーン樹脂におけるシロキサン構成単位の全量に対するエポキシ基を有する構成単位の割合が50モル%以上であり、数平均分子量が1000〜3000であるシリコーン樹脂である。本明細書では、上記カチオン硬化性シリコーン樹脂を、「本発明のカチオン硬化性シリコーン樹脂」と称する場合がある。
測定装置:商品名「JNM−ECA500NMR」(日本電子(株)製)
溶媒:重クロロホルム
積算回数:1800回
測定温度:25℃
測定装置:商品名「FT−720」((株)堀場製作所製)
測定方法:透過法
分解能:4cm-1
測定波数域:400〜4000cm-1
積算回数:16回
測定装置:商品名「LC−20AD」((株)島津製作所製)
カラム:Shodex KF−801×2本、KF−802、及びKF−803(昭和電工(株)製)
測定温度:40℃
溶離液:THF、試料濃度0.1〜0.2重量%
流量:1mL/分
検出器:UV−VIS検出器(商品名「SPD−20A」、(株)島津製作所製)
分子量:標準ポリスチレン換算
本発明の実施態様1では、本発明のカチオン硬化性シリコーン樹脂以外のエポキシ化合物を含む。本発明の硬化性組成物は、本発明のカチオン硬化性シリコーン樹脂に加えて、エポキシ化合物を含む場合、高い表面硬度を有し、可とう性及び加工性に優れた硬化物を形成できる。
本発明の実施態様2では、水酸基、カルボキシル基、及びエポキシ基からなる群から選択される少なくとも1つの基を有する(メタ)アクリル酸エステル系樹脂を含む。上記(メタ)アクリル酸エステル系樹脂は、(メタ)アクリル酸エステル系樹脂の主鎖又は側鎖の一部に、水酸基、カルボキシル基、及びエポキシ基からなる群から選択される少なくとも1つの基を有する。
本発明の硬化性組成物は、レベリング剤を必須成分として含む。本発明の硬化性組成物は、レベリング剤を含むことにより、本発明の硬化性組成物の表面張力を低下させることができ、また、硬化物の表面硬度が向上する。特に、レベリング剤を本発明のカチオン硬化性シリコーン樹脂と組み合わせて用いることにより、硬化物の表面を平滑化し、透明性、光沢等の外観、滑り性を向上することができる。さらに、特定のレベリング剤を用いることにより、硬化物の表面硬度、耐擦傷性がより向上し、配合割合を制御することによりさらに向上させることができる。
本発明の硬化性組成物は、本発明のカチオン硬化性シリコーン樹脂、及びレベリング剤を必須成分として含む硬化性組成物(硬化性樹脂組成物)である。後述のように、本発明の硬化性組成物は、さらに、硬化触媒(特に光カチオン重合開始剤)や表面調整剤あるいは表面改質剤等のその他の成分を含んでいてもよい。
本発明の硬化性組成物におけるカチオン硬化性化合物(本発明のカチオン硬化性シリコーン樹脂、エポキシ化合物等)の重合反応を進行させることにより、該硬化性組成物を硬化させることができ、硬化物(「本発明の硬化物」と称する場合がある)を得ることができる。硬化の方法は、周知の方法より適宜選択でき、特に限定されないが、例えば、活性エネルギー線の照射、及び/又は、加熱する方法が挙げられる。上記活性エネルギー線としては、例えば、赤外線、可視光線、紫外線、X線、電子線、α線、β線、γ線等のいずれを使用することもできる。中でも、取り扱い性に優れる点で、紫外線が好ましい。
本発明のハードコート層(即ち、本発明の硬化性組成物を硬化させて得られた硬化物で形成されたハードコート層)を少なくとも有する成形体を、「本発明の成形体」と称する場合がある。本発明の成形体は、本発明のハードコート層のみから形成されていてもよいし、部材の表面に本発明のハードコート層が積層された成形体であってもよい。
(カチオン硬化性シリコーン樹脂の調製)
温度計、攪拌装置、還流冷却器、及び窒素導入管を取り付けた300ミリリットルのフラスコ(反応容器)に、窒素気流下で2−(3,4−エポキシシクロヘキシル)エチルトリメトキシシラン(以下、「EMS」と称する)161.5ミリモル(39.79g)、フェニルトリメトキシシラン(以下、「PMS」と称する)9ミリモル(1.69g)、及びアセトン165.9gを仕込み、50℃に昇温した。このようにして得られた混合物に、5%炭酸カリウム水溶液4.70g(炭酸カリウムとして1.7ミリモル)を5分で滴下した後、水1700ミリモル(30.60g)を20分かけて滴下した。なお、滴下の間、著しい温度上昇は起こらなかった。その後、50℃のまま、重縮合反応を窒素気流下で4時間行った。
重縮合反応後の反応溶液中の生成物を分析したところ、数平均分子量は1911であり、分子量分散度は1.47であった。上記生成物の29Si−NMRスペクトルから算出されるT2体とT3体のモル比[T3体/T2体]は10.3であった。
その後、反応溶液を冷却し、下層液が中性になるまで水洗を行い、上層液を分取した後、1mmHg、40℃の条件で上層液から溶媒を留去し、無色透明の液状の生成物(エポキシ基を有するシルセスキオキサン単位を含むカチオン硬化性シリコーン樹脂)を得た。上記生成物のTd5は370℃であった。
得られたカチオン硬化性シリコーン樹脂(以下、「硬化性樹脂A」と称する)4.5重量部、エポキシ化合物0.5重量部、MEK1.3重量部、光カチオン重合開始剤0.1重量部、レベリング剤0.05重量部の混合溶液を作製し、これをハードコート液(硬化性組成物)として使用した。
得られたハードコート液を、ワイヤーバー#30を用いてPETフィルムの表面に塗布した後、70℃のオーブンで1分間放置(プレベイク)し、次いで、高圧水銀ランプ(アイグラフィックス(株)製)を用いて、400mJ/cm2の照射量で紫外線を5秒間照射した。その後、15℃で1時間熱処理(エージング処理)することによってハードコート液の塗工膜を硬化させ、ハードコート層を有するハードコートフィルムを作製した。
ハードコート液(硬化性組成物)の組成及びハードコート層の厚みを表1に示すように変更したこと以外は実施例1と同様にして、ハードコート液を作製した。該ハードコート液を使用し、ハードコート層の厚みを表1に示すように変更したこと以外は実施例1と同様にして、ハードコートフィルムを作製した。なお、表1に記載の硬化性組成物の原料の配合量の単位は、重量部である。
(カチオン硬化性シリコーン樹脂の調製)
温度計、攪拌装置、還流冷却器、及び窒素導入管を取り付けた300ミリリットルのフラスコ(反応容器)に、窒素気流下でEMS161.5ミリモル(39.79g)、PMS9ミリモル(1.69g)、及びアセトン165.9gを仕込み、50℃に昇温した。このようにして得られた混合物に、5%炭酸カリウム水溶液4.70g(炭酸カリウムとして1.7ミリモル)を5分で滴下した後、水1700ミリモル(30.60g)を20分かけて滴下した。なお、滴下の間、著しい温度上昇は起こらなかった。その後、50℃のまま、重縮合反応を窒素気流下で4時間行った。
重縮合反応後の反応溶液中の生成物を分析したところ、数平均分子量は1799であり、分子量分散度は1.57であった。上記生成物の29Si−NMRスペクトルから算出されるT2体とT3体のモル比[T3体/T2体]は10.1であった。
その後、反応溶液を冷却し、下層液が中性になるまで水洗を行い、上層液を分取した後、1mmHg、40℃の条件で上層液から溶媒を留去し、無色透明の液状の生成物(エポキシ基を有するシルセスキオキサン単位を含むカチオン硬化性シリコーン樹脂)を得た。上記生成物のTd5は370℃であった。
得られたカチオン硬化性シリコーン樹脂(以下、「硬化性樹脂B」と称する)4.5重量部、エポキシ化合物0.5重量部、光カチオン重合開始剤0.05重量部、レベリング剤0.05重量部の混合溶液を作製し、これをハードコート液(硬化性組成物)として使用した。
得られたハードコート液を、ワイヤーバー#30を用いてPETフィルムの表面に塗布した後、70℃のオーブンで1分間放置(プレベイク)し、次いで、高圧水銀ランプ(アイグラフィックス(株)製)を用いて、400mJ/cm2の照射量で紫外線を5秒間照射した。その後、15℃で1時間熱処理(エージング処理)することによってハードコート液の塗工膜を硬化させ、ハードコート層を有するハードコートフィルムを作製した。
ハードコート液(硬化性組成物)の組成及びハードコート層の厚みを表1に示すように変更したこと以外は実施例5と同様にして、ハードコート液を作製した。該ハードコート液を使用し、ハードコート層の厚みを表1に示すように変更したこと以外は実施例5と同様にして、ハードコートフィルムを作製した。なお、表1に記載の硬化性組成物の原料の配合量の単位は、重量部である。
ハードコート液(硬化性組成物)の組成及びハードコート層の厚みを表2に示すように変更したこと以外は実施例1と同様にして、ハードコート液を作製した。該ハードコート液を使用し、ハードコート層の厚みを表2に示すように変更したこと以外は実施例1と同様にして、ハードコートフィルムを作製した。実施例8〜13で得られたポリオルガノシルセスキオキサンのFT−IRスペクトルを上述の方法で測定したところ、いずれも1100cm-1付近に一つの固有吸収ピークを有することが確認された。なお、表2に記載の硬化性組成物の原料の配合量の単位は、重量部である。
上記で得たハードコートフィルムの耐屈曲性を、円筒形マンドレルを使用してJIS K5600−5−1に準じて評価した。結果を、表1及び2の「マンドレル試験(mm)」の欄に示した。
上記で得たハードコートフィルムにおけるハードコート層表面の鉛筆硬度を、JIS K5600−5−4に準じて評価した。評価を3回行い、最も硬いものを評価結果とした。結果を、表1及び2の「鉛筆硬度」の欄に示した。
(エポキシ化合物)
セロキサイド2021P:商品名「セロキサイド2021P」[3,4−エポキシシクロヘキシルメチル(3,4−エポキシ)シクロヘキサンカルボキシレート]、(株)ダイセル製
エポキシ化合物A:ビス(3,4−エポキシシクロヘキシルメチル)エーテル
EHPE3150:商品名「EHPE3150」(2,2−ビス(ヒドロキシメチル)−1−ブタノールの1,2−エポキシ−4−(2−オキシラニル)シクロヘキサン付加物)、(株)ダイセル製
エポキシ化合物B:2,2−ビス(3,4−エポキシシクロヘキシルメチル)プロパン
(溶剤)
MEK:メチルエチルケトン
(硬化性樹脂)
PETIA:ペンタエリスリトールトリアクリレートとペンタエリスリトールテトラアクリレートの混合物、商品名「PETIA」(ダイセル・オルネクス(株)製)
IRR214K:トリシクロデカンジメタノールジアクリレート、商品名「IRR214K」(ダイセル・オルネクス(株)製)
TA−100:アクリルシリコーン樹脂、商品名「SQ TA−100」(東亜合成(株)製)
SI−20:アクリルシリコーン樹脂、商品名「SQ SI−20」(東亜合成(株)製)
(アクリル酸エステル系樹脂)
SG−600 TEA:アクリル酸エステル共重合体(官能基としてOH基を有する)、商品名「SG−600 TEA」(ナガセケムテックス(株)製)
SG−280 EK23:アクリル酸エステル共重合体(官能基としてCOOH基を有する)、商品名「SG−280 EK23」(ナガセケムテックス(株)製)
SG−P3:アクリル酸エステル共重合体(官能基としてエポキシ基を有する)、商品名「SG−P3」(ナガセケムテックス(株)製)
(光カチオン重合開始剤)
WPI−124:商品名「WPI−124」、和光純薬工業(株)製、光酸発生剤の50%溶液
硬化触媒A:[4−(4−ビフェニルチオ)フェニル]−4−ビフェニルフェニルスルホニウム トリス(ペンタフルオロエチル)トリフルオロホスフェートのプロピレングリコールメチルエーテルアセテート50%溶液
イルガキュア 184:光重合開始剤、商品名「IRGACURE 184」(BASFジャパン(株)製)
(レベリング剤)
サーフロン S−243:商品名「サーフロン S−243」、フッ素化合物のエチレンオキサイド付加物、AGCセイミケミカル(株)製
Claims (11)
- カチオン硬化性シリコーン樹脂、
前記カチオン硬化性シリコーン樹脂以外のエポキシ化合物、
及びレベリング剤を含有し、
前記カチオン硬化性シリコーン樹脂が、シルセスキオキサン単位を含み、前記カチオン硬化性シリコーン樹脂におけるシロキサン構成単位の全量に対するエポキシ基を有する構成単位の割合が50モル%以上であり、数平均分子量が1000〜3000であるシリコーン樹脂であることを特徴とする硬化性組成物。 - 前記エポキシ化合物が、脂環式エポキシ化合物である請求項1に記載の硬化性組成物。
- 前記エポキシ化合物が、シクロヘキセンオキシド基を有する化合物である請求項1又は2に記載の硬化性組成物。
- カチオン硬化性シリコーン樹脂、
水酸基、カルボキシル基、及びエポキシ基からなる群から選択される少なくとも1つの基を有する(メタ)アクリル酸エステル系樹脂、
及びレベリング剤を含み、
前記カチオン硬化性シリコーン樹脂が、単量体を構成する単位としてシルセスキオキサン単位を含み、全単量体単位のうちエポキシ基を有する単量体単位の割合が、50モル%以上であり、且つ数平均分子量が、1000〜3000である硬化性組成物。 - 前記(メタ)アクリル酸エステル系樹脂の割合が、前記カチオン硬化性シリコーン樹脂100重量部に対して、0.1〜20重量部である請求項4に記載の硬化性組成物。
- 前記カチオン硬化性シリコーン樹脂の分子量分散度(重量平均分子量/数平均分子量)が1.0〜3.0である請求項1〜8のいずれか1項に記載の硬化性組成物。
- 前記レベリング剤が、シリコーン系レベリング剤及びフッ素系レベリング剤からなる群より選択される1種以上のレベリング剤であり、かつエポキシ基と反応性を有する基及び加水分解縮合性基からなる群より選択される1種以上の基を有する請求項1〜9のいずれか1項に記載の硬化性組成物。
- 請求項1〜10のいずれか1項に記載の硬化性組成物の硬化物で形成されたハードコート層を有する成形体。
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