JP5430095B2 - Curable resin composition - Google Patents
Curable resin composition Download PDFInfo
- Publication number
- JP5430095B2 JP5430095B2 JP2008206649A JP2008206649A JP5430095B2 JP 5430095 B2 JP5430095 B2 JP 5430095B2 JP 2008206649 A JP2008206649 A JP 2008206649A JP 2008206649 A JP2008206649 A JP 2008206649A JP 5430095 B2 JP5430095 B2 JP 5430095B2
- Authority
- JP
- Japan
- Prior art keywords
- resin composition
- weight
- curable resin
- acryloyl
- thermoplastic resin
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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- 239000011342 resin composition Substances 0.000 title claims description 50
- -1 acryloyl compound Chemical group 0.000 claims description 51
- 229920005989 resin Polymers 0.000 claims description 32
- 239000011347 resin Substances 0.000 claims description 32
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 claims description 27
- 229920005992 thermoplastic resin Polymers 0.000 claims description 27
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 18
- 125000004430 oxygen atom Chemical group O* 0.000 claims description 18
- 239000003505 polymerization initiator Substances 0.000 claims description 12
- 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 claims description 10
- 125000004432 carbon atom Chemical group C* 0.000 claims description 10
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 9
- 125000004429 atom Chemical group 0.000 claims description 9
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 9
- 239000001257 hydrogen Substances 0.000 claims description 9
- 229910052739 hydrogen Inorganic materials 0.000 claims description 9
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 9
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 9
- 125000001570 methylene group Chemical group [H]C([H])([*:1])[*:2] 0.000 claims description 9
- 229910052757 nitrogen Inorganic materials 0.000 claims description 9
- 229910052760 oxygen Inorganic materials 0.000 claims description 9
- 239000001301 oxygen Substances 0.000 claims description 9
- 229910052717 sulfur Inorganic materials 0.000 claims description 9
- 239000011593 sulfur Substances 0.000 claims description 9
- 229920003229 poly(methyl methacrylate) Polymers 0.000 claims description 8
- 239000004926 polymethyl methacrylate Substances 0.000 claims description 8
- 125000001424 substituent group Chemical group 0.000 claims description 8
- MPIAGWXWVAHQBB-UHFFFAOYSA-N [3-prop-2-enoyloxy-2-[[3-prop-2-enoyloxy-2,2-bis(prop-2-enoyloxymethyl)propoxy]methyl]-2-(prop-2-enoyloxymethyl)propyl] prop-2-enoate Chemical compound C=CC(=O)OCC(COC(=O)C=C)(COC(=O)C=C)COCC(COC(=O)C=C)(COC(=O)C=C)COC(=O)C=C MPIAGWXWVAHQBB-UHFFFAOYSA-N 0.000 claims description 7
- XLPJNCYCZORXHG-UHFFFAOYSA-N 1-morpholin-4-ylprop-2-en-1-one Chemical compound C=CC(=O)N1CCOCC1 XLPJNCYCZORXHG-UHFFFAOYSA-N 0.000 claims description 5
- RESPXSHDJQUNTN-UHFFFAOYSA-N 1-piperidin-1-ylprop-2-en-1-one Chemical compound C=CC(=O)N1CCCCC1 RESPXSHDJQUNTN-UHFFFAOYSA-N 0.000 claims description 4
- WLPAQAXAZQUXBG-UHFFFAOYSA-N 1-pyrrolidin-1-ylprop-2-en-1-one Chemical compound C=CC(=O)N1CCCC1 WLPAQAXAZQUXBG-UHFFFAOYSA-N 0.000 claims description 4
- 125000001931 aliphatic group Chemical group 0.000 claims description 4
- 125000003118 aryl group Chemical group 0.000 claims description 4
- 239000003999 initiator Substances 0.000 claims description 4
- AKVUWTYSNLGBJY-UHFFFAOYSA-N 2-methyl-1-morpholin-4-ylprop-2-en-1-one Chemical compound CC(=C)C(=O)N1CCOCC1 AKVUWTYSNLGBJY-UHFFFAOYSA-N 0.000 claims description 3
- FDSUVTROAWLVJA-UHFFFAOYSA-N 2-[[3-hydroxy-2,2-bis(hydroxymethyl)propoxy]methyl]-2-(hydroxymethyl)propane-1,3-diol;prop-2-enoic acid Chemical compound OC(=O)C=C.OC(=O)C=C.OC(=O)C=C.OC(=O)C=C.OC(=O)C=C.OCC(CO)(CO)COCC(CO)(CO)CO FDSUVTROAWLVJA-UHFFFAOYSA-N 0.000 claims description 2
- 239000006096 absorbing agent Substances 0.000 claims description 2
- 230000009477 glass transition Effects 0.000 claims description 2
- 150000002148 esters Chemical class 0.000 claims 2
- 229920001169 thermoplastic Polymers 0.000 claims 2
- 239000004416 thermosoftening plastic Substances 0.000 claims 2
- 229920000058 polyacrylate Polymers 0.000 claims 1
- 229920000193 polymethacrylate Polymers 0.000 claims 1
- 239000010410 layer Substances 0.000 description 37
- 238000012360 testing method Methods 0.000 description 15
- 239000010408 film Substances 0.000 description 14
- 238000000034 method Methods 0.000 description 13
- 238000007666 vacuum forming Methods 0.000 description 9
- 238000000576 coating method Methods 0.000 description 8
- 239000000203 mixture Substances 0.000 description 8
- 238000005299 abrasion Methods 0.000 description 7
- 229920006289 polycarbonate film Polymers 0.000 description 7
- 239000000126 substance Substances 0.000 description 7
- 238000000465 moulding Methods 0.000 description 5
- 239000004417 polycarbonate Substances 0.000 description 5
- 239000000758 substrate Substances 0.000 description 5
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 4
- 239000004431 polycarbonate resin Substances 0.000 description 4
- 229920005668 polycarbonate resin Polymers 0.000 description 4
- 239000002904 solvent Substances 0.000 description 4
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 3
- WMYINDVYGQKYMI-UHFFFAOYSA-N 2-[2,2-bis(hydroxymethyl)butoxymethyl]-2-ethylpropane-1,3-diol Chemical compound CCC(CO)(CO)COCC(CC)(CO)CO WMYINDVYGQKYMI-UHFFFAOYSA-N 0.000 description 3
- LWRBVKNFOYUCNP-UHFFFAOYSA-N 2-methyl-1-(4-methylsulfanylphenyl)-2-morpholin-4-ylpropan-1-one Chemical compound C1=CC(SC)=CC=C1C(=O)C(C)(C)N1CCOCC1 LWRBVKNFOYUCNP-UHFFFAOYSA-N 0.000 description 3
- 229920000178 Acrylic resin Polymers 0.000 description 3
- 239000004925 Acrylic resin Substances 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 125000005396 acrylic acid ester group Chemical group 0.000 description 3
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 3
- 229910052782 aluminium Inorganic materials 0.000 description 3
- ISAOCJYIOMOJEB-UHFFFAOYSA-N benzoin Chemical compound C=1C=CC=CC=1C(O)C(=O)C1=CC=CC=C1 ISAOCJYIOMOJEB-UHFFFAOYSA-N 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 description 3
- 229920000515 polycarbonate Polymers 0.000 description 3
- 238000012546 transfer Methods 0.000 description 3
- 239000012956 1-hydroxycyclohexylphenyl-ketone Substances 0.000 description 2
- KUIZKZHDMPERHR-UHFFFAOYSA-N 1-phenylprop-2-en-1-one Chemical compound C=CC(=O)C1=CC=CC=C1 KUIZKZHDMPERHR-UHFFFAOYSA-N 0.000 description 2
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 description 2
- ZNQVEEAIQZEUHB-UHFFFAOYSA-N 2-ethoxyethanol Chemical compound CCOCCO ZNQVEEAIQZEUHB-UHFFFAOYSA-N 0.000 description 2
- NJWGQARXZDRHCD-UHFFFAOYSA-N 2-methylanthraquinone Chemical compound C1=CC=C2C(=O)C3=CC(C)=CC=C3C(=O)C2=C1 NJWGQARXZDRHCD-UHFFFAOYSA-N 0.000 description 2
- KWOLFJPFCHCOCG-UHFFFAOYSA-N Acetophenone Chemical compound CC(=O)C1=CC=CC=C1 KWOLFJPFCHCOCG-UHFFFAOYSA-N 0.000 description 2
- DKPFZGUDAPQIHT-UHFFFAOYSA-N Butyl acetate Natural products CCCCOC(C)=O DKPFZGUDAPQIHT-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 2
- 229920004142 LEXAN™ Polymers 0.000 description 2
- 239000004418 Lexan Substances 0.000 description 2
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 2
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 2
- 239000004743 Polypropylene Substances 0.000 description 2
- 239000004793 Polystyrene Substances 0.000 description 2
- 229920000297 Rayon Polymers 0.000 description 2
- 244000028419 Styrax benzoin Species 0.000 description 2
- 235000000126 Styrax benzoin Nutrition 0.000 description 2
- 235000008411 Sumatra benzointree Nutrition 0.000 description 2
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 description 2
- 239000002250 absorbent Substances 0.000 description 2
- 230000002745 absorbent Effects 0.000 description 2
- 125000003647 acryloyl group Chemical group O=C([*])C([H])=C([H])[H] 0.000 description 2
- 150000001412 amines Chemical class 0.000 description 2
- 229960002130 benzoin Drugs 0.000 description 2
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 description 2
- MQDJYUACMFCOFT-UHFFFAOYSA-N bis[2-(1-hydroxycyclohexyl)phenyl]methanone Chemical compound C=1C=CC=C(C(=O)C=2C(=CC=CC=2)C2(O)CCCCC2)C=1C1(O)CCCCC1 MQDJYUACMFCOFT-UHFFFAOYSA-N 0.000 description 2
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000007865 diluting Methods 0.000 description 2
- 239000003085 diluting agent Substances 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 238000007756 gravure coating Methods 0.000 description 2
- 235000019382 gum benzoic Nutrition 0.000 description 2
- FUZZWVXGSFPDMH-UHFFFAOYSA-N hexanoic acid Chemical compound CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 description 2
- HJOVHMDZYOCNQW-UHFFFAOYSA-N isophorone Chemical compound CC1=CC(=O)CC(C)(C)C1 HJOVHMDZYOCNQW-UHFFFAOYSA-N 0.000 description 2
- 239000004611 light stabiliser Substances 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- XNLICIUVMPYHGG-UHFFFAOYSA-N pentan-2-one Chemical compound CCCC(C)=O XNLICIUVMPYHGG-UHFFFAOYSA-N 0.000 description 2
- 229920003023 plastic Polymers 0.000 description 2
- 239000004033 plastic Substances 0.000 description 2
- 239000005020 polyethylene terephthalate Substances 0.000 description 2
- 229920000139 polyethylene terephthalate Polymers 0.000 description 2
- 238000006116 polymerization reaction Methods 0.000 description 2
- 229920001155 polypropylene Polymers 0.000 description 2
- 229920002223 polystyrene Polymers 0.000 description 2
- 239000004800 polyvinyl chloride Substances 0.000 description 2
- 229920000915 polyvinyl chloride Polymers 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 239000002964 rayon Substances 0.000 description 2
- 238000007493 shaping process Methods 0.000 description 2
- 239000007921 spray Substances 0.000 description 2
- 239000006097 ultraviolet radiation absorber Substances 0.000 description 2
- QNODIIQQMGDSEF-UHFFFAOYSA-N (1-hydroxycyclohexyl)-phenylmethanone Chemical compound C=1C=CC=CC=1C(=O)C1(O)CCCCC1 QNODIIQQMGDSEF-UHFFFAOYSA-N 0.000 description 1
- MSAHTMIQULFMRG-UHFFFAOYSA-N 1,2-diphenyl-2-propan-2-yloxyethanone Chemical compound C=1C=CC=CC=1C(OC(C)C)C(=O)C1=CC=CC=C1 MSAHTMIQULFMRG-UHFFFAOYSA-N 0.000 description 1
- ALVZNPYWJMLXKV-UHFFFAOYSA-N 1,9-Nonanediol Chemical compound OCCCCCCCCCO ALVZNPYWJMLXKV-UHFFFAOYSA-N 0.000 description 1
- LNOUMTOCQWMBOJ-UHFFFAOYSA-N 1-(1,3-benzodioxol-5-yl)prop-2-en-1-one Chemical compound C=CC(=O)C1=CC=C2OCOC2=C1 LNOUMTOCQWMBOJ-UHFFFAOYSA-N 0.000 description 1
- TYMZHOWAEZZPOR-UHFFFAOYSA-N 1-(2-hydroxyphenyl)prop-2-en-1-one Chemical compound OC1=CC=CC=C1C(=O)C=C TYMZHOWAEZZPOR-UHFFFAOYSA-N 0.000 description 1
- MLKIVXXYTZKNMI-UHFFFAOYSA-N 1-(4-dodecylphenyl)-2-hydroxy-2-methylpropan-1-one Chemical compound CCCCCCCCCCCCC1=CC=C(C(=O)C(C)(C)O)C=C1 MLKIVXXYTZKNMI-UHFFFAOYSA-N 0.000 description 1
- ZBOSXTFCZNZKEE-UHFFFAOYSA-N 1-(4-ethoxyphenyl)prop-2-en-1-one Chemical compound CCOC1=CC=C(C(=O)C=C)C=C1 ZBOSXTFCZNZKEE-UHFFFAOYSA-N 0.000 description 1
- SUSMVZKZAWLRLB-UHFFFAOYSA-N 1-(4-ethylpiperazin-1-yl)prop-2-en-1-one Chemical compound CCN1CCN(C(=O)C=C)CC1 SUSMVZKZAWLRLB-UHFFFAOYSA-N 0.000 description 1
- YVNNRQCAABDUMX-UHFFFAOYSA-N 1-(4-methylpiperazin-1-yl)prop-2-en-1-one Chemical compound CN1CCN(C(=O)C=C)CC1 YVNNRQCAABDUMX-UHFFFAOYSA-N 0.000 description 1
- RHLXKNKGQYNPCQ-UHFFFAOYSA-N 1-(4-phenylpiperazin-1-yl)prop-2-en-1-one Chemical compound C1CN(C(=O)C=C)CCN1C1=CC=CC=C1 RHLXKNKGQYNPCQ-UHFFFAOYSA-N 0.000 description 1
- XSTBLQWORDGVAQ-UHFFFAOYSA-N 1-(4-propylpiperazin-1-yl)prop-2-en-1-one Chemical compound CCCN1CCN(C(=O)C=C)CC1 XSTBLQWORDGVAQ-UHFFFAOYSA-N 0.000 description 1
- HMWAJFNEGAJETK-UHFFFAOYSA-N 1-[6-(dimethylamino)naphthalen-2-yl]prop-2-en-1-one Chemical compound C1=C(C(=O)C=C)C=CC2=CC(N(C)C)=CC=C21 HMWAJFNEGAJETK-UHFFFAOYSA-N 0.000 description 1
- JLBXCKSMESLGTJ-UHFFFAOYSA-N 1-ethoxypropan-1-ol Chemical compound CCOC(O)CC JLBXCKSMESLGTJ-UHFFFAOYSA-N 0.000 description 1
- LHENQXAPVKABON-UHFFFAOYSA-N 1-methoxypropan-1-ol Chemical compound CCC(O)OC LHENQXAPVKABON-UHFFFAOYSA-N 0.000 description 1
- ZOZCGSOVPRABJM-UHFFFAOYSA-N 1-piperidin-1-ylprop-2-en-1-one;1-pyrrolidin-1-ylprop-2-en-1-one Chemical compound C=CC(=O)N1CCCC1.C=CC(=O)N1CCCCC1 ZOZCGSOVPRABJM-UHFFFAOYSA-N 0.000 description 1
- LYGXUCWNFYFFBS-UHFFFAOYSA-N 1-thiomorpholin-4-ylprop-2-en-1-one Chemical compound C=CC(=O)N1CCSCC1 LYGXUCWNFYFFBS-UHFFFAOYSA-N 0.000 description 1
- BRKORVYTKKLNKX-UHFFFAOYSA-N 2,4-di(propan-2-yl)thioxanthen-9-one Chemical compound C1=CC=C2C(=O)C3=CC(C(C)C)=CC(C(C)C)=C3SC2=C1 BRKORVYTKKLNKX-UHFFFAOYSA-N 0.000 description 1
- LCHAFMWSFCONOO-UHFFFAOYSA-N 2,4-dimethylthioxanthen-9-one Chemical compound C1=CC=C2C(=O)C3=CC(C)=CC(C)=C3SC2=C1 LCHAFMWSFCONOO-UHFFFAOYSA-N 0.000 description 1
- LCZVSXRMYJUNFX-UHFFFAOYSA-N 2-[2-(2-hydroxypropoxy)propoxy]propan-1-ol Chemical compound CC(O)COC(C)COC(C)CO LCZVSXRMYJUNFX-UHFFFAOYSA-N 0.000 description 1
- FGTYTUFKXYPTML-UHFFFAOYSA-N 2-benzoylbenzoic acid Chemical compound OC(=O)C1=CC=CC=C1C(=O)C1=CC=CC=C1 FGTYTUFKXYPTML-UHFFFAOYSA-N 0.000 description 1
- KMNCBSZOIQAUFX-UHFFFAOYSA-N 2-ethoxy-1,2-diphenylethanone Chemical compound C=1C=CC=CC=1C(OCC)C(=O)C1=CC=CC=C1 KMNCBSZOIQAUFX-UHFFFAOYSA-N 0.000 description 1
- SJEBAWHUJDUKQK-UHFFFAOYSA-N 2-ethylanthraquinone Chemical compound C1=CC=C2C(=O)C3=CC(CC)=CC=C3C(=O)C2=C1 SJEBAWHUJDUKQK-UHFFFAOYSA-N 0.000 description 1
- QPXVRLXJHPTCPW-UHFFFAOYSA-N 2-hydroxy-2-methyl-1-(4-propan-2-ylphenyl)propan-1-one Chemical compound CC(C)C1=CC=C(C(=O)C(C)(C)O)C=C1 QPXVRLXJHPTCPW-UHFFFAOYSA-N 0.000 description 1
- BQZJOQXSCSZQPS-UHFFFAOYSA-N 2-methoxy-1,2-diphenylethanone Chemical compound C=1C=CC=CC=1C(OC)C(=O)C1=CC=CC=C1 BQZJOQXSCSZQPS-UHFFFAOYSA-N 0.000 description 1
- RUMACXVDVNRZJZ-UHFFFAOYSA-N 2-methylpropyl 2-methylprop-2-enoate Chemical compound CC(C)COC(=O)C(C)=C RUMACXVDVNRZJZ-UHFFFAOYSA-N 0.000 description 1
- KTALPKYXQZGAEG-UHFFFAOYSA-N 2-propan-2-ylthioxanthen-9-one Chemical compound C1=CC=C2C(=O)C3=CC(C(C)C)=CC=C3SC2=C1 KTALPKYXQZGAEG-UHFFFAOYSA-N 0.000 description 1
- YTPSFXZMJKMUJE-UHFFFAOYSA-N 2-tert-butylanthracene-9,10-dione Chemical compound C1=CC=C2C(=O)C3=CC(C(C)(C)C)=CC=C3C(=O)C2=C1 YTPSFXZMJKMUJE-UHFFFAOYSA-N 0.000 description 1
- FRIBMENBGGCKPD-UHFFFAOYSA-N 3-(2,3-dimethoxyphenyl)prop-2-enal Chemical compound COC1=CC=CC(C=CC=O)=C1OC FRIBMENBGGCKPD-UHFFFAOYSA-N 0.000 description 1
- JSGVZVOGOQILFM-UHFFFAOYSA-N 3-methoxy-1-butanol Chemical compound COC(C)CCO JSGVZVOGOQILFM-UHFFFAOYSA-N 0.000 description 1
- CCTFMNIEFHGTDU-UHFFFAOYSA-N 3-methoxypropyl acetate Chemical compound COCCCOC(C)=O CCTFMNIEFHGTDU-UHFFFAOYSA-N 0.000 description 1
- KBEJLPDEPRDDRN-UHFFFAOYSA-N 3-prop-2-enoyl-1,3-oxazolidin-2-id-4-one Chemical compound C(C=C)(=O)N1[CH-]OCC1=O KBEJLPDEPRDDRN-UHFFFAOYSA-N 0.000 description 1
- HIBSYUPTCGGRSD-UHFFFAOYSA-N 3-prop-2-enoyl-1,3-oxazolidin-2-one Chemical compound C=CC(=O)N1CCOC1=O HIBSYUPTCGGRSD-UHFFFAOYSA-N 0.000 description 1
- 239000004342 Benzoyl peroxide Substances 0.000 description 1
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 description 1
- JMOQWLCDVSEMIK-UHFFFAOYSA-N C1=CC=C2N(C)C(C(=O)C=C)=CC2=C1 Chemical compound C1=CC=C2N(C)C(C(=O)C=C)=CC2=C1 JMOQWLCDVSEMIK-UHFFFAOYSA-N 0.000 description 1
- MINUEAIONSTPBY-UHFFFAOYSA-N C=CC(=O)C1CCCCC1=C Chemical compound C=CC(=O)C1CCCCC1=C MINUEAIONSTPBY-UHFFFAOYSA-N 0.000 description 1
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 1
- 101000720524 Gordonia sp. (strain TY-5) Acetone monooxygenase (methyl acetate-forming) Proteins 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-M Methacrylate Chemical compound CC(=C)C([O-])=O CERQOIWHTDAKMF-UHFFFAOYSA-M 0.000 description 1
- 229920002292 Nylon 6 Polymers 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 239000004372 Polyvinyl alcohol Substances 0.000 description 1
- 229920001328 Polyvinylidene chloride Polymers 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- GUCYFKSBFREPBC-UHFFFAOYSA-N [phenyl-(2,4,6-trimethylbenzoyl)phosphoryl]-(2,4,6-trimethylphenyl)methanone Chemical compound CC1=CC(C)=CC(C)=C1C(=O)P(=O)(C=1C=CC=CC=1)C(=O)C1=C(C)C=C(C)C=C1C GUCYFKSBFREPBC-UHFFFAOYSA-N 0.000 description 1
- 229920000122 acrylonitrile butadiene styrene Polymers 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 150000001338 aliphatic hydrocarbons Chemical class 0.000 description 1
- 150000004056 anthraquinones Chemical class 0.000 description 1
- 239000002216 antistatic agent Substances 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 150000008365 aromatic ketones Chemical class 0.000 description 1
- RWCCWEUUXYIKHB-UHFFFAOYSA-N benzophenone Chemical compound C=1C=CC=CC=1C(=O)C1=CC=CC=C1 RWCCWEUUXYIKHB-UHFFFAOYSA-N 0.000 description 1
- 239000012965 benzophenone Substances 0.000 description 1
- 235000019400 benzoyl peroxide Nutrition 0.000 description 1
- RSOILICUEWXSLA-UHFFFAOYSA-N bis(1,2,2,6,6-pentamethylpiperidin-4-yl) decanedioate Chemical compound C1C(C)(C)N(C)C(C)(C)CC1OC(=O)CCCCCCCCC(=O)OC1CC(C)(C)N(C)C(C)(C)C1 RSOILICUEWXSLA-UHFFFAOYSA-N 0.000 description 1
- 230000000903 blocking effect Effects 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 229920006026 co-polymeric resin Polymers 0.000 description 1
- 239000011247 coating layer Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- SZXQTJUDPRGNJN-UHFFFAOYSA-N dipropylene glycol Chemical compound OCCCOCCCO SZXQTJUDPRGNJN-UHFFFAOYSA-N 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000010292 electrical insulation Methods 0.000 description 1
- 229920006351 engineering plastic Polymers 0.000 description 1
- UHESRSKEBRADOO-UHFFFAOYSA-N ethyl carbamate;prop-2-enoic acid Chemical compound OC(=O)C=C.CCOC(N)=O UHESRSKEBRADOO-UHFFFAOYSA-N 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 239000012760 heat stabilizer Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- XXMIOPMDWAUFGU-UHFFFAOYSA-N hexane-1,6-diol Chemical compound OCCCCCCO XXMIOPMDWAUFGU-UHFFFAOYSA-N 0.000 description 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 125000005647 linker group Chemical group 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000000691 measurement method Methods 0.000 description 1
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 1
- 229910052753 mercury Inorganic materials 0.000 description 1
- 125000005641 methacryl group Chemical group 0.000 description 1
- 125000002816 methylsulfanyl group Chemical group [H]C([H])([H])S[*] 0.000 description 1
- SLCVBVWXLSEKPL-UHFFFAOYSA-N neopentyl glycol Chemical compound OCC(C)(C)CO SLCVBVWXLSEKPL-UHFFFAOYSA-N 0.000 description 1
- 239000012788 optical film Substances 0.000 description 1
- MPQXHAGKBWFSNV-UHFFFAOYSA-N oxidophosphanium Chemical class [PH3]=O MPQXHAGKBWFSNV-UHFFFAOYSA-N 0.000 description 1
- 150000002923 oximes Chemical class 0.000 description 1
- NWVVVBRKAWDGAB-UHFFFAOYSA-N p-methoxyphenol Chemical compound COC1=CC=C(O)C=C1 NWVVVBRKAWDGAB-UHFFFAOYSA-N 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 229920001490 poly(butyl methacrylate) polymer Polymers 0.000 description 1
- 229920003207 poly(ethylene-2,6-naphthalate) Polymers 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 239000011112 polyethylene naphthalate Substances 0.000 description 1
- 229920005672 polyolefin resin Polymers 0.000 description 1
- 229920002451 polyvinyl alcohol Polymers 0.000 description 1
- 239000005033 polyvinylidene chloride Substances 0.000 description 1
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 239000012748 slip agent Substances 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- CIHOLLKRGTVIJN-UHFFFAOYSA-N tert‐butyl hydroperoxide Chemical compound CC(C)(C)OO CIHOLLKRGTVIJN-UHFFFAOYSA-N 0.000 description 1
- UWHCKJMYHZGTIT-UHFFFAOYSA-N tetraethylene glycol Chemical compound OCCOCCOCCOCCO UWHCKJMYHZGTIT-UHFFFAOYSA-N 0.000 description 1
- 229920001187 thermosetting polymer Polymers 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
Landscapes
- Polymerisation Methods In General (AREA)
- Graft Or Block Polymers (AREA)
Description
本発明は、表面硬度が高く、耐摩耗性、耐擦傷性に優れると共に、熱成形性に優れた硬化物を生成する硬化性樹脂組成物に関するものである。 The present invention relates to a curable resin composition having a high surface hardness, excellent wear resistance and scratch resistance, and producing a cured product having excellent thermoformability.
ポリカーボネート樹脂、アクリル樹脂、ポリオレフィン樹脂等からなる樹脂成型品は、軽量で、透明性、耐衝撃性、成形性に優れており、レンズや光学フィルム、各種メータユニットの保護カバー、電気製品の外装部等に広く利用されている。 Resin molded products made of polycarbonate resin, acrylic resin, polyolefin resin, etc. are lightweight and have excellent transparency, impact resistance, and moldability. Lenses, optical films, protective covers for various meter units, exterior parts for electrical products Widely used.
例えばポリカーボネート樹脂は、透明性、耐衝撃性、電気絶縁性、難燃性に優れており、車両のヘッドライトや風防、建築物の外壁板、携帯機器の筐体等に利用されるが、表面硬度が低く、耐摩耗性、耐擦傷性に劣るという欠点を有する。そのため、上記樹脂成型品は表面に紫外線硬化樹脂等からなるハードコート層を形成し、耐摩耗性を改善することが提案されている（特許文献１）。 For example, polycarbonate resin has excellent transparency, impact resistance, electrical insulation, and flame retardancy, and is used for vehicle headlights and windshields, building outer wall plates, portable device casings, etc. It has the disadvantages of low hardness and inferior wear resistance and scratch resistance. For this reason, it has been proposed that the resin molded product is formed with a hard coat layer made of an ultraviolet curable resin or the like on the surface to improve the wear resistance (Patent Document 1).
しかし、従来のハードコート層は、伸度が小さいため熱成形性に劣るという欠点を有する。すなわち、ポリカーボネート樹脂からなる成型品の表面にハードコート層を設け、更に二次成形加工した場合、ハードコート層が、基体であるポリカーボネート樹脂の変形に追従できずに白濁やクラックが発生してしまう。 However, the conventional hard coat layer has a drawback that it has poor thermoformability due to its low elongation. That is, when a hard coat layer is provided on the surface of a molded product made of polycarbonate resin and further subjected to secondary molding, the hard coat layer cannot follow the deformation of the polycarbonate resin as a substrate, and white turbidity and cracks are generated. .
本発明は、上記問題に鑑みてなされたものであり、表面硬度が高く、耐摩耗性、耐擦傷性に優れると共に熱成形性に優れた硬化物を生成する硬化性樹脂組成物を提供することを目的とする。 The present invention has been made in view of the above problems, and provides a curable resin composition that generates a cured product having high surface hardness, excellent wear resistance and scratch resistance, and excellent thermoformability. With the goal.
本発明者らは、鋭意研究した結果、下記式Ｉで示されるアクリロイル化合物を少なくとも１種以上と、多官能性アクリル酸エステルを少なくとも１種類以上と、熱可塑性樹脂と、重合開始剤とを含有することを特徴とする硬化性樹脂組成物が、表面硬度が高く、耐摩耗性、耐擦傷性に優れると共に熱成形性に優れた硬化物を生成することを見出した。 As a result of diligent research, the present inventors have found that at least one acryloyl compound represented by the following formula I, at least one polyfunctional acrylate ester, a thermoplastic resin, and a polymerization initiator are contained. It has been found that the curable resin composition characterized in that it produces a cured product having high surface hardness, excellent wear resistance and scratch resistance, and excellent thermoformability.
下記式Ｉで示されるアクリロイル化合物を少なくとも１種以上と、多官能性アクリル酸エステルを少なくとも１種類以上と、熱可塑性樹脂と、重合開始剤とを含有することを特徴とする硬化性樹脂組成物は、表面硬度が高く、耐摩耗性、耐擦傷性に優れると共に熱成形性に優れた硬化物を生成する。従って、本発明における前記硬化性樹脂組成物から生成する硬化物を樹脂成型品のハードコート層として用いた場合、容易に二次成形加工することができる。 A curable resin composition comprising at least one acryloyl compound represented by the following formula I, at least one polyfunctional acrylate ester, a thermoplastic resin, and a polymerization initiator. Produces a cured product having high surface hardness, excellent wear resistance and scratch resistance, and excellent thermoformability. Therefore, when the hardened | cured material produced | generated from the said curable resin composition in this invention is used as a hard-coat layer of a resin molded product, it can carry out a secondary shaping | molding process easily.
また、下記式Ｉで示されるアクリロイル化合物を少なくとも１種以上と、多官能性アクリル酸エステルを少なくとも１種類以上と、熱可塑性樹脂と、重合開始剤とを含有することを特徴とする硬化性樹脂組成物は、表面硬度が高く、耐摩耗性、耐擦傷性に優れると共に熱成形性に優れた硬化物を生成する。従って、本発明における前記硬化性樹脂組成物から生成する硬化物を樹脂成型品のハードコート層として用いた場合、容易に二次成形加工することができる。 A curable resin comprising at least one acryloyl compound represented by the following formula I, at least one polyfunctional acrylate ester, a thermoplastic resin, and a polymerization initiator. The composition has a high surface hardness, is excellent in wear resistance and scratch resistance, and produces a cured product excellent in thermoformability. Therefore, when the hardened | cured material produced | generated from the said curable resin composition in this invention is used as a hard-coat layer of a resin molded product, it can carry out a secondary shaping | molding process easily.
本発明における硬化性樹脂組成物は、下記式Ｉで示されるアクリロイル化合物を少なくとも１種以上と、多官能性アクリル酸エステルを少なくとも１種以上と、熱可塑性樹脂と、重合開始剤とを含有するものである。 The curable resin composition in the present invention contains at least one acryloyl compound represented by the following formula I, at least one polyfunctional acrylate, a thermoplastic resin, and a polymerization initiator. Is.
また、本発明における硬化性樹脂組成物は、下記式Ｉで示されるアクリロイル化合物を少なくとも１種以上と、多官能性アクリル酸エステルを少なくとも１種以上と、熱可塑性樹脂と、重合開始剤とを含有するものである。 Moreover, the curable resin composition in the present invention comprises at least one acryloyl compound represented by the following formula I, at least one polyfunctional acrylate ester, a thermoplastic resin, and a polymerization initiator. It contains.
本願におけるアクリロイル化合物とは、下記式Ｉで示されるようにアクリロイル基を有するものである。 The acryloyl compound in the present application has an acryloyl group as shown by the following formula I.
ここで、連結基Ｙが有していても良い置換基としては、＝Ｏ、−ＯＨ、−ＣＨ３、−ＣＨ２ＣＨ３等が挙げられるがこれらに限定されるものではない。 Here, examples of the substituent that the linking group Y may have include, but are not limited to, ═O, —OH, —CH 3 , —CH 2 CH 3, and the like.
本発明における硬化性樹脂組成物から硬度の高い硬化物を得るには、前記式Ｉで示されるアクリロイル化合物が有する置換基Ｚが、炭素数４〜２０の脂肪族環もしくは芳香族環であるアクリロイル化合物を用いることが好ましい。 In order to obtain a cured product having high hardness from the curable resin composition of the present invention, the acryloyl compound represented by the above formula I has an acryloyl group in which the substituent Z is an aliphatic or aromatic ring having 4 to 20 carbon atoms. It is preferable to use a compound.
前記アクリロイル化合物の具体例としては、アクリロイルモルフォリン、メタアクリロイルモルフォリン、アクリロダン、１−アクリロイルピロリジン、１−アクリロイルピペリジン、４−アクリロイルチオモルフォリン、アクリロフェノン、２−アクリロイルフェノール、１−アクリロイル−４−メチルピペラジン、１−アクリロイル−４−エチルピペラジン、１−アクリロイル−４−フェニルピペラジン、１−アクリロイル−４−プロピルピペラジン、３‐アクリロイルオキサゾリジン‐２‐オン、２−アクリロイル−１−メチル−１Ｈ−インドール、４’−エトキシアクリロフェノン、５−アクリロイル−１，３−ベンゾジオキソール、１−アクリロイル−２−メチレンシクロへキサン、１−アクリロイル−２−メチレンシクロへプタン、３−アクリロイル−２−オキサゾリドン、アクリロイルベンゼンが挙げられるがこれらに限定されるものではない。これらの中でも、アクリロイルモルフォリン、メタアクリロイルモルフォリン、アクリロイルピロリジン、アクリロイルピペリジンが好ましい。 Specific examples of the acryloyl compound include acryloylmorpholine, methacryloylmorpholine, acrylodan, 1-acryloylpyrrolidine, 1-acryloylpiperidine, 4-acryloylthiomorpholine, acrylophenone, 2-acryloylphenol, 1-acryloyl- 4-methylpiperazine, 1-acryloyl-4-ethylpiperazine, 1-acryloyl-4-phenylpiperazine, 1-acryloyl-4-propylpiperazine, 3-acryloyloxazolidine-2-one, 2-acryloyl-1-methyl-1H Indole, 4′-ethoxyacrylophenone, 5-acryloyl-1,3-benzodioxole, 1-acryloyl-2-methylenecyclohexane, 1-acryloyl-2-methylenecyclohepta , 3-acryloyl-2-oxazolidone, do not including but acryloyl benzene limited thereto. Among these, acryloyl morpholine, methacryloyl morpholine, acryloyl pyrrolidine, and acryloyl piperidine are preferable.
本願における多官能性アクリル酸エステルは、分子内に重合性官能基を２以上有するものである、本願における多官能性アクリル酸エステルの具体例としては、１，４−ブタンジオールジ（メタ）アクリレート、１，６−ヘキサンジオールジ（メタ）アクリレート、１，９−ノナンジオールジ（メタ）アクリレート、ネオペンチルグリコールジ（メタ）アクリレート、ジプロピレングリコールジ（メタ）アクリレート、トリプロピレングリコールジ（メタ）アクリレート、テトラエチレングリコールジ（メタ）アクリレート、トリメチロールプロパンジ（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、ペンタエリスリトールジ（メタ）アクリレート、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、ジトリメチロールプロパンジ（メタ）アクリレート、ジトリメチロールプロパントリ（メタ）アクリレート、ジトリメチロールプロパンテトラ（メタ）アクリレート、ジペンタエリスリトールジ（メタ）アクリレート、ジペンタエリスリトールトリ（メタ）アクリレート、ジ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ペンタ（メタ）アクリレート、ジペンタエリスリトールヘキサ（メタ）アクリレート等が挙げられるが、これらに限定されるものではない。なかでも、ジペンタエリスリトールジアクリレート、ジペンタエリスリトールトリアクリレート、ジペンタエリスリトールテトラアクリレート、ジペンタエリスリトールペンタアクリレート、ジペンタエリスリトールヘキサアクリレートが好ましい。 The polyfunctional acrylic ester in the present application has two or more polymerizable functional groups in the molecule. Specific examples of the polyfunctional acrylic ester in the present application include 1,4-butanediol di (meth) acrylate. 1,6-hexanediol di (meth) acrylate, 1,9-nonanediol di (meth) acrylate, neopentyl glycol di (meth) acrylate, dipropylene glycol di (meth) acrylate, tripropylene glycol di (meth) Acrylate, tetraethylene glycol di (meth) acrylate, trimethylolpropane di (meth) acrylate, trimethylolpropane tri (meth) acrylate, pentaerythritol di (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol Ritolol tetra (meth) acrylate, ditrimethylolpropane di (meth) acrylate, ditrimethylolpropane tri (meth) acrylate, ditrimethylolpropane tetra (meth) acrylate, dipentaerythritol di (meth) acrylate, dipentaerythritol tri (meth) acrylate , Dipentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, and the like, but are not limited thereto. Of these, dipentaerythritol diacrylate, dipentaerythritol triacrylate, dipentaerythritol tetraacrylate, dipentaerythritol pentaacrylate, and dipentaerythritol hexaacrylate are preferable.
なお、本願において「（メタ）アクリル」とは、「メタアクリル」または「アクリル」を示す。同様に、本願において「（メタ）アクリレート」とは、「メタアクリレート」または「アクリレート」を示す。 In the present application, “(meth) acryl” means “methacryl” or “acryl”. Similarly, in the present application, “(meth) acrylate” means “methacrylate” or “acrylate”.
本願における熱可塑性樹脂としては、ポリエチレン、ポリプロピレン、ポリ塩化ビニル、ポリスチレン、ＡＳ樹脂、ＡＢＳ樹脂、ポリエチレンテレフタレート、アクリル樹脂、ポリビニルアルコール、ポリ塩化ビニリデン等を用いることができる。本発明における硬化性樹脂組成物を樹脂成型品のハードコート層として使用する場合、樹脂成型品との密着性を考慮して、熱可塑性樹脂を適宜選択して使用することが可能である。特に、本発明における硬化性樹脂組成物をポリカーボネートからなる樹脂成型品のハードコート層として用いる場合には、熱可塑性樹脂としてポリメチルメタクリレート（ＰＭＭＡ）を用いることが好ましく、特に、重量平均分子量１００，０００〜４００，０００のポリメチルメタクリレート（ＰＭＭＡ）を用いることが好ましい。 As the thermoplastic resin in the present application, polyethylene, polypropylene, polyvinyl chloride, polystyrene, AS resin, ABS resin, polyethylene terephthalate, acrylic resin, polyvinyl alcohol, polyvinylidene chloride, and the like can be used. When the curable resin composition in the present invention is used as a hard coat layer of a resin molded product, it is possible to appropriately select and use a thermoplastic resin in consideration of adhesion to the resin molded product. In particular, when the curable resin composition in the present invention is used as a hard coat layer of a resin molded product made of polycarbonate, it is preferable to use polymethyl methacrylate (PMMA) as a thermoplastic resin, and in particular, a weight average molecular weight of 100, It is preferable to use 000 to 400,000 polymethyl methacrylate (PMMA).
本願における熱可塑性樹脂は、ガラス転移温度（Ｔｇ）が３０〜１１０℃であるものを用いることが好ましい。本発明の硬化性樹脂組成物において、Ｔｇが３０℃未満の熱可塑性樹脂を用いると、硬化物の硬度が不足する場合があり好ましくない。一方、本発明の硬化性樹脂組成物において、Ｔｇが１１０℃を超える熱可塑性樹脂を用いると、熱成形性が低い硬化物が生成する場合があり好ましくない。 The thermoplastic resin in the present application preferably has a glass transition temperature (Tg) of 30 to 110 ° C. In the curable resin composition of the present invention, if a thermoplastic resin having a Tg of less than 30 ° C. is used, the hardness of the cured product may be insufficient. On the other hand, in the curable resin composition of the present invention, when a thermoplastic resin having a Tg of more than 110 ° C. is used, a cured product having low thermoformability may be generated, which is not preferable.
本発明における硬化性樹脂組成物において、下記式Ｉで示されるアクリロイル化合物、多官能性アクリル酸エステルおよび熱可塑性樹脂の配合量を合計１００重量％とした時に、前記アクリロイル化合物を３０〜７０重量％、多官能性アクリル酸エステルを２０〜４０重量％、および熱可塑性樹脂を５〜３５重量％の範囲で含有させることが好ましい。 In the curable resin composition in the present invention, when the total amount of the acryloyl compound represented by the following formula I, the polyfunctional acrylate ester and the thermoplastic resin is 100% by weight, the acryloyl compound is 30 to 70% by weight. The polyfunctional acrylic acid ester is preferably contained in an amount of 20 to 40% by weight and the thermoplastic resin in an amount of 5 to 35% by weight.
本発明における硬化性樹脂組成物において、上記式Ｉで示されるアクリロイル化合物、多官能性アクリル酸エステルおよび熱可塑性樹脂の配合量を合計１００重量％とした時に、前記アクリロイル化合物の含有量が３０重量％未満の組成物を硬化させた場合、熱成形性が低い硬化物が生成することがあり好ましくない。すなわち、前記アクリロイル化合物の含有量が３０重量％未満の硬化性樹脂組成物の硬化物を、樹脂成型品のハードコート層として用いると、二次成形加工時にハードコート層が基材の変形に追従できず白濁やクラックが生じることがあり好ましくない。一方、本発明の硬化性樹脂組成物において、前記アクリロイル化合物の含有量が７０重量％を超える組成物を硬化させた場合、表面硬度の低い硬化物が生成することがあり好ましくない。すなわち、前記アクリロイル化合物の含有量が７０重量％を超える硬化性樹脂組成物の硬化物を、樹脂成型品のハードコート層として用いると、表面硬度が低く、耐摩耗性、耐擦傷性が劣るため樹脂成型品が傷つくことがあり好ましくない。 In the curable resin composition of the present invention, when the total amount of the acryloyl compound represented by the formula I, the polyfunctional acrylate ester and the thermoplastic resin is 100% by weight, the content of the acryloyl compound is 30% by weight. When a composition of less than% is cured, a cured product having low thermoformability may be generated, which is not preferable. That is, when a cured product of a curable resin composition having a content of the acryloyl compound of less than 30% by weight is used as a hard coat layer of a resin molded product, the hard coat layer follows the deformation of the substrate during the secondary molding process. It may not be possible to cause cloudiness or cracks, which is not preferable. On the other hand, in the curable resin composition of the present invention, when a composition in which the content of the acryloyl compound exceeds 70% by weight is cured, a cured product having a low surface hardness may be generated, which is not preferable. That is, when a cured product of a curable resin composition having a content of the acryloyl compound exceeding 70% by weight is used as a hard coat layer of a resin molded product, the surface hardness is low, and the wear resistance and scratch resistance are inferior. The resin molded product may be damaged, which is not preferable.
本発明における硬化性樹脂組成物において、多官能性アクリル酸エステルの含有量が２０重量％未満の組成物を硬化させた場合、表面硬度の低い硬化物が生成することがあり好ましくない。すなわち、多官能性アクリル酸エステルの含有量が２０重量％未満の硬化性樹脂組成物の硬化物を、樹脂成型品のハードコート層として用いると、表面硬度が低く、耐摩耗性、耐擦傷性が劣るため樹脂成型品が傷つくことがあり好ましくない。一方、本発明の硬化性樹脂組成物において、多官能性アクリル酸エステルの含有量が４０重量％を超える組成物を硬化させた場合、熱成形性が低い硬化物が生成することがあり好ましくない。すなわち、多官能性アクリル酸エステルの含有量が４０重量％を超える硬化性樹脂組成物の硬化物を、樹脂成型品のハードコート層として用いると、二次成形加工時にハードコート層が基材の変形に追従できず白濁やクラックが生じることがあり好ましくない。 In the curable resin composition of the present invention, when a composition having a polyfunctional acrylic ester content of less than 20% by weight is cured, a cured product having a low surface hardness may be generated, which is not preferable. That is, when a cured product of a curable resin composition having a polyfunctional acrylic ester content of less than 20% by weight is used as a hard coat layer of a resin molded product, the surface hardness is low, and the wear resistance and scratch resistance are reduced. Is not preferable because the resin molded product may be damaged. On the other hand, in the curable resin composition of the present invention, when a composition having a polyfunctional acrylic acid ester content exceeding 40% by weight is cured, a cured product having low thermoformability may be generated, which is not preferable. . That is, when a cured product of a curable resin composition having a polyfunctional acrylic ester content exceeding 40% by weight is used as a hard coat layer of a resin molded product, the hard coat layer is used as a base material during secondary molding processing. It is not preferable because it cannot follow the deformation and may cause cloudiness or cracks.
また、本発明における硬化性樹脂組成物において、熱可塑性樹脂の含有量が５重量％未満の組成物を硬化させた場合、基材との密着性が劣ることがあり好ましくない。すなわち、熱可塑性樹脂の含有量が５重量％未満の硬化性樹脂組成物の硬化物を、樹脂成型品のハードコート層として用いると、樹脂成型品との密着性が低いためハードコート層が剥離し易くなることがあり好ましくない。特に、このようなハードコート層を設けた樹脂成型品を二次加工する場合、基材の変形に伴ってハードコート層が剥離することがあり好ましくない。一方、熱可塑性樹脂の含有量が３５重量％を超える硬化性樹脂組成物を硬化させた場合、硬度の低い硬化物が生成することがあり好ましくない。すなわち、熱硬化性樹脂の含有量が３５重量％を超える硬化性樹脂組成物の硬化物を、樹脂成型品のハードコート層として用いると、表面硬度が低く、耐摩耗性、耐擦傷性に劣るため樹脂成型品が傷つくことがあり好ましくない。 Further, in the curable resin composition of the present invention, when a composition having a thermoplastic resin content of less than 5% by weight is cured, the adhesion with the substrate may be inferior, which is not preferable. That is, when a cured product of a curable resin composition having a thermoplastic resin content of less than 5% by weight is used as a hard coat layer of a resin molded product, the hard coat layer peels off due to low adhesion to the resin molded product. This is not preferable because it can be easily performed. In particular, when a resin molded product provided with such a hard coat layer is subjected to secondary processing, the hard coat layer may be peeled off as the substrate is deformed, which is not preferable. On the other hand, when a curable resin composition having a thermoplastic resin content exceeding 35% by weight is cured, a cured product having low hardness may be generated, which is not preferable. That is, when a cured product of a curable resin composition having a thermosetting resin content exceeding 35% by weight is used as a hard coat layer of a resin molded product, the surface hardness is low, and the wear resistance and scratch resistance are poor. Therefore, the resin molded product may be damaged, which is not preferable.
本願における重合開始剤としては、公知のものを単独でもしくは組み合わせて使用することができ、例えば、過酸化ベンゾイル、アゾビスイソブチロニトリル、キュメンハイドロパーオキサイト、ｔ−ブチルハイドロパーオキサイト等の熱重合開始剤、或いはベンゾイン、ベンゾインメチルエーテル、ベンゾインエチルエーテル、ベンゾインイソプロピルエーテル等のベンゾイン又はベンゾインアルキルエーテル類、ベンゾフェノン、ベンゾイル安息香酸等の芳香族ケトン類、ベンジル等のアルファ−ジカルボニル類、ベンジルジメチルケタール、ベンジルジエチルケタール等のベンジルケタール類、アセトフェノン、１−（４−ドデシルフェニル）−２−ヒドロキシ−２−メチルプロパン−１−オン、１−ヒドロキシシクロヘキシルフェニルケトン、２−ヒドロキシ−２−メチル−１−フェニル−１−プロパン−１−オン、１−（４−イソプロピルフェニル）−２−ヒドロキシ−２−メチル−プロパン−１−オン、２−メチル−１−〔４−（メチルチオ）フェニル〕−２−モルホリノプロパノン−１等のアセトフェノン類、２−メチルアントラキノン、２−エチルアントラキノン、２−ｔ−ブチルアントラキノン等のアントラキノン類、２、４−ジメチルチオキサントン、２−イソプロピルチオキサントン、２、４−ジイソプロピルチオキサントン等のチオキサントン類、ビス（２、４、６−トリメチルベンゾイル）−フェニルフォスフィンオキサイド等のフォスヒンオキサイド類、１−フェニル−１、２−プロパンジオン−２−（ｏ−エトキシカルボニル）オキシム等のアルファ−アシルオキシム類、ｐ−ジメチルアミノ安息香酸エチル、ｐ−ジメチルアミノ安息香酸イソアミル等のアミン類の光重合開始剤を使用することができるが、これらに限定されるものではない。 As a polymerization initiator in this application, a well-known thing can be used individually or in combination, for example, benzoyl peroxide, azobisisobutyronitrile, cumene hydroperoxide, t-butyl hydroperoxide, etc. Benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin alkyl ethers such as benzoin isopropyl ether, aromatic ketones such as benzophenone and benzoylbenzoic acid, and alpha-dicarbonyls such as benzyl, Benzyl ketals such as benzyl dimethyl ketal and benzyl diethyl ketal, acetophenone, 1- (4-dodecylphenyl) -2-hydroxy-2-methylpropan-1-one, 1-hydroxycyclohexyl phenyl Ketone, 2-hydroxy-2-methyl-1-phenyl-1-propan-1-one, 1- (4-isopropylphenyl) -2-hydroxy-2-methyl-propan-1-one, 2-methyl-1 Acetophenones such as-[4- (methylthio) phenyl] -2-morpholinopropanone-1, anthraquinones such as 2-methylanthraquinone, 2-ethylanthraquinone, 2-t-butylanthraquinone, 2,4-dimethylthioxanthone, Thioxanthones such as 2-isopropylthioxanthone, 2,4-diisopropylthioxanthone, Phosphine oxides such as bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide, 1-phenyl-1,2-propanedione- Alphas such as 2- (o-ethoxycarbonyl) oxime - acyl oximes, p- dimethylaminobenzoic acid ethyl, p- an amine such as dimethyl amino benzoic acid isoamyl a photopolymerization initiator can be used, but is not limited thereto.
本発明における硬化性樹脂組成物が含有する重合開始剤としては、生産効率が良く、また、低温で反応し、耐熱性のない基材への塗工ができる点から光重合開始剤を用いることが好ましい。 As the polymerization initiator contained in the curable resin composition in the present invention, a photopolymerization initiator is used from the viewpoint of good production efficiency, reaction at a low temperature, and application to a non-heat-resistant substrate. Is preferred.
重合開始剤の添加量としては、上記式Ｉで示されるアクリロイル化合物、多官能性アクリル酸エステル、および熱可塑性樹脂の合計１００重量部に対し、１〜１０重量部用いることが好ましい。 The addition amount of the polymerization initiator is preferably 1 to 10 parts by weight with respect to 100 parts by weight in total of the acryloyl compound represented by the above formula I, the polyfunctional acrylic acid ester, and the thermoplastic resin.
また、本発明における硬化性樹脂組成物は、所望により、重合調整剤、光安定剤、紫外線吸収剤、熱安定剤、スリップ剤、帯電防止剤等の各種添加剤を含有させることができる。 Moreover, the curable resin composition in this invention can contain various additives, such as a polymerization regulator, a light stabilizer, a ultraviolet absorber, a heat stabilizer, a slip agent, and an antistatic agent, if desired.
本発明における硬化性樹脂組成物に紫外線吸収剤を含有させる場合、耐久性を考慮すると反応性紫外線吸収剤を用いることが好ましい。前記反応性紫外線吸収剤の具体例としては、反応性ＵＶＡであるＲＵＶＡ−９３（大塚化学製）が挙げられるが、これに限定されるものではない。 When the ultraviolet absorbent is contained in the curable resin composition in the present invention, it is preferable to use a reactive ultraviolet absorbent in consideration of durability. Specific examples of the reactive ultraviolet absorber include, but are not limited to, RUVA-93 (manufactured by Otsuka Chemical) which is reactive UVA.
本発明における硬化性樹脂組成物は、所望により希釈溶剤で希釈、溶解して調製することができる。前記希釈溶剤としては、例えばヘキサン、ヘプタン、シクロヘキサンなどの脂肪族炭化水素、トルエン、キシレンなどの芳香族炭化水素、メタノール、エタノール、プロパノール、イソプロパノール、ブタノールなどのアルコール、メチルエチルケトン、２−ぺンタノン、イソホロンなどのケトン、酢酸エチル、酢酸ブチル、酢酸メトキシプロピルなどのエステル、エチルセロソルブなどのセロソルブ系溶剤、メトキシプロパノール、エトキシプロパノール、メトキシブタノールなどのグリコール系溶剤を単独又は混合して使用できるが、これらに限定されるものではない。 The curable resin composition in the present invention can be prepared by diluting and dissolving with a diluting solvent as desired. Examples of the diluent solvent include aliphatic hydrocarbons such as hexane, heptane and cyclohexane, aromatic hydrocarbons such as toluene and xylene, alcohols such as methanol, ethanol, propanol, isopropanol and butanol, methyl ethyl ketone, 2-pentanone and isophorone. Such as ketone, ethyl acetate, butyl acetate, methoxypropyl acetate, etc., cellosolve solvent such as ethyl cellosolve, glycol solvent such as methoxypropanol, ethoxypropanol, methoxybutanol etc. can be used alone or in combination. It is not limited.
本発明における硬化性樹脂組成物は、ディッピング法、フローコート法、スプレー法、バーコード法、グラビアコート法、ロールコート法、ブレードコート法、エアーナイフ法等の方法で樹脂成型品の表面に塗布し、乾燥、硬化させてハードコート層とすることができる。 The curable resin composition in the present invention is applied to the surface of a resin molded product by a dipping method, a flow coating method, a spray method, a barcode method, a gravure coating method, a roll coating method, a blade coating method, an air knife method or the like. Then, it can be dried and cured to form a hard coat layer.
また、予め本発明の硬化性樹脂組成物を用いてフィルムを作製し、これを樹脂成型品に貼着してハードコート層を形成しても良い。この場合、まず基材フィルム上に、本発明における硬化性樹脂組成物を、フローコート法、スプレー法、バーコード法、グラビアコート法、ロールコート法、ブレードコート法、エアーナイフ法等の方法で塗布し、乾燥後、硬化させてハードコート層転写フィルムを作製する。その後、このハードコート層転写フィルムを使用して、ハードコート層を樹脂成型品に転写する。上記基材フィルムとしては、ポリエチレンテレフタレート、ポリエチレンナフタレート、ナイロン６、ポリプロピレン、ポリ塩化ビニル、ポリメチルメタクリレート、ポリカーボネート、ポリスチレン等の樹脂からなるフィルムを使用することができるが、これらに限定されるものではない。 Alternatively, a film may be prepared in advance using the curable resin composition of the present invention, and this may be attached to a resin molded product to form a hard coat layer. In this case, first, the curable resin composition according to the present invention is first applied onto the base film by a method such as a flow coating method, a spray method, a barcode method, a gravure coating method, a roll coating method, a blade coating method, or an air knife method. It is applied, dried and cured to produce a hard coat layer transfer film. Thereafter, the hard coat layer transfer film is used to transfer the hard coat layer to a resin molded product. As the base film, a film made of a resin such as polyethylene terephthalate, polyethylene naphthalate, nylon 6, polypropylene, polyvinyl chloride, polymethyl methacrylate, polycarbonate, polystyrene or the like can be used, but is not limited thereto. is not.
本発明における硬化性樹脂組成物を樹脂成型品のハードコート層として使用する場合、ハードコート層の厚みを１〜１５μｍとすることが好ましい。樹脂成型品の二次加工性を考えると、ハードコート層の厚みを１〜１０μｍとすることがより好ましく、２〜６μｍとすることが特に好ましい。 When using the curable resin composition in this invention as a hard-coat layer of a resin molded product, it is preferable that the thickness of a hard-coat layer shall be 1-15 micrometers. Considering the secondary workability of the resin molded product, the thickness of the hard coat layer is more preferably 1 to 10 μm, and particularly preferably 2 to 6 μm.
以下、実施例により本発明をさらに具体的に説明するが、本発明はこれら実施例に何ら限定されるものではない。 EXAMPLES Hereinafter, the present invention will be described more specifically with reference to examples. However, the present invention is not limited to these examples.
[特性の測定方法および効果の評価方法]
本発明における特性の測定方法及び評価方法は次の通りである。
[Characteristic measurement method and effect evaluation method]
The characteristic measuring method and evaluation method in the present invention are as follows.
（１）鉛筆硬度試験
以下のとおり、ハードコート層を有するポリカーボネートフィルムを用いて鉛筆硬度試験を行った。ＪＩＳ Ｋ−５６００準拠の安田精機製の鉛筆硬度試験機：Ｎｏ．５５３に三菱鉛筆製の鉛筆硬度試験用鉛筆を装着し、荷重７５０ｇ、引っ掻き角度４５°、引っ掻き速度０．５ｍｍ／分にてハードコード層表面の鉛筆硬度試験を実施した。
(1) Pencil hardness test The pencil hardness test was done using the polycarbonate film which has a hard-coat layer as follows. Pencil hardness tester manufactured by Yasuda Seiki in accordance with JIS K-5600: A pencil hardness test pencil made by Mitsubishi Pencil was attached to 553, and a pencil hardness test on the surface of the hard cord layer was performed at a load of 750 g, a scratch angle of 45 °, and a scratch speed of 0.5 mm / min.
（２）テーバー磨耗試験
以下のとおり、ハードコート層を有するポリカーボネートフィルムを用いてテーバー摩耗試験を行った。テーバー磨耗試験機（東洋精機製、ＭＯＤＥＬ５１３０）に摩耗輪ＣＳ１０Ｆを取り付け、加重５００ｇで実施例１のハードコート層表面で１００回転させた。ガードナー社製ヘイズガードII（ＪＩＳ Ｋ７３６１［ＩＳＯ法：積分球補償あり］）を使用して、摩耗試験前後におけるヘイズ値の変化を測定した。
(2) Taber abrasion test The Taber abrasion test was done using the polycarbonate film which has a hard-coat layer as follows. A wear wheel CS10F was attached to a Taber abrasion tester (Model 5130, manufactured by Toyo Seiki Co., Ltd.) and rotated 100 times on the surface of the hard coat layer of Example 1 at a load of 500 g. The change in haze value before and after the wear test was measured using Gardner's haze guard II (JIS K7361 [ISO method: with integrating sphere compensation]).
（３）真空成形試験
熱成形性を評価するために以下のとおり真空成形試験を行った。真空成形機：（成光産業（株）製 「フォーミング４８０型」）に、ハードコート層を有するポリカーボネートフィルム、および図１に示すような最大絞り深さ１５ｍｍのアルミ製金型をセットし、ヒーターを３８０℃まで昇温させた。次いで、フィルムとヒーターとの距離を１０ｃｍに設定し２５秒間加熱すると、フィルム表面の温度が１５０℃以上になりフィルムが軟化した。この状態で、真空ポンプを用いてフィルムを吸引しながら、反対側からフィルムにアルミ製金型を密着させ、絞り深さ１５ｍｍの真空成形試験を行った。
(3) Vacuum forming test In order to evaluate thermoformability, a vacuum forming test was performed as follows. Vacuum forming machine: (Forming 480 type made by Seiko Sangyo Co., Ltd.) A polycarbonate film having a hard coat layer and an aluminum mold having a maximum drawing depth of 15 mm as shown in FIG. The temperature was raised to 380 ° C. Subsequently, when the distance between the film and the heater was set to 10 cm and heating was performed for 25 seconds, the temperature of the film surface became 150 ° C. or more, and the film was softened. In this state, while sucking the film using a vacuum pump, an aluminum mold was brought into close contact with the film from the opposite side, and a vacuum forming test with a drawing depth of 15 mm was performed.
（実施例１）
硬化性樹脂組成物の調製
紫外線遮断環境下、以下の手順にて硬化性樹脂組成物を調製した。攪拌機を備えたステンレス製の容器に、紫外線吸収剤 ＲＵＶＡ−９３（大塚化学製：反応性ＵＶＡ）１．８ｇ、ヒンダードアミン系光安定剤 チヌビン２９２（チバスペシャリティケミカル製）０．９ｇ、シリコン系表面調整剤ＢＹＫ−３０６（ビッグケミー製）０．６ｇ、熱可塑性樹脂 ＬＲ−２４８（三菱レイヨン製：アクリル樹脂３０％溶液）４９．３ｇ（１５重量％）、重合禁止剤 ハイドロキノンモノメチルエーテル０．０９ｇ、希釈溶剤として酢酸ブチル１４８ｇおよびイソプロパノール３６．９ｇを投入し、液温度を３０〜３５℃に保ちながら、１５分間攪拌し均一溶液とした。
Example 1
Preparation of curable resin composition A curable resin composition was prepared in the following procedure under an ultraviolet blocking environment. In a stainless steel container equipped with a stirrer, 1.8 g of UV absorber RUVA-93 (manufactured by Otsuka Chemical: Reactive UVA), hindered amine light stabilizer Tinuvin 292 (manufactured by Ciba Specialty Chemicals), 0.9 g of silicon surface adjustment Agent BYK-306 (manufactured by Big Chemie) 0.6 g, thermoplastic resin LR-248 (manufactured by Mitsubishi Rayon: acrylic resin 30% solution) 49.3 g (15% by weight), polymerization inhibitor hydroquinone monomethyl ether 0.09 g, diluent solvent 148 g of butyl acetate and 36.9 g of isopropanol were added, and the mixture was stirred for 15 minutes while maintaining the liquid temperature at 30 to 35 ° C. to obtain a uniform solution.
さらに、上記溶液に、多官能性アクリル酸エステルとしてＤＰＨＡ（ジペンタエリスリトールヘキサアクリレート：日本化薬製）を３４．６ｇ（３５重量％）、アクリロイル化合物としてアクリロイルモルフォリン（興人製）を４９．５ｇ（５０重量％）、光重合開始剤 Ｉｒｇａｃｕｒｅ９０７（チバスペシャリティケミカル製）を２．２５ｇ投入し、液温度を３０〜３５℃に保ちながら１５分間攪拌し、硬化性樹脂組成物を得た。 Furthermore, 34.6 g (35% by weight) of DPHA (dipentaerythritol hexaacrylate: manufactured by Nippon Kayaku Co., Ltd.) as a polyfunctional acrylate ester and 49. acryloylmorpholine (manufactured by Kojin Co., Ltd.) as an acryloyl compound were added to the above solution. 5 g (50 wt%) and 2.25 g of photopolymerization initiator Irgacure 907 (manufactured by Ciba Specialty Chemicals) were added and stirred for 15 minutes while maintaining the liquid temperature at 30 to 35 ° C. to obtain a curable resin composition.
硬化物の作製
グラビアコーターにて６０メッシュグラビアロールを用い、塗工速度１０ｍ／ｍｉｎになるように設定し、厚さ１８０μｍのポリカーボネートフィルム（サビックイノベーティブプラスチックス製 レキサンＰＣ）に上述の硬化性樹脂組成物を連続塗工した。塗工後、フィルムを８０℃で約２分間熱風乾燥させ、高圧水銀ランプによる積算光量１２００ｍｊ／ｃｍ２となるよう紫外線照射を行い硬化させて、ポリカーボネートフィルム上にハードコート層を形成した。このときハードコート層の厚みは３μｍであった。
Preparation of cured product Using a 60 mesh gravure roll with a gravure coater, the coating speed was set to 10 m / min, and the above-mentioned curable resin was applied to a polycarbonate film (Lexan PC made by Subic Innovative Plastics) with a thickness of 180 μm. The composition was continuously applied. After the coating, the film was dried with hot air at 80 ° C. for about 2 minutes, and irradiated with ultraviolet rays so as to obtain an integrated light amount of 1200 mj / cm 2 with a high-pressure mercury lamp, and hard coating layer was formed on the polycarbonate film. At this time, the thickness of the hard coat layer was 3 μm.
（実施例２〜９）
表１に示した配合の硬化性樹脂組成物を用いた以外は、実施例１と同様にしてポリカーボネートフィルム上にハードコート層を形成し実施例２〜９とした。
(Examples 2-9)
Except having used the curable resin composition of the mixing | blending shown in Table 1, it carried out similarly to Example 1, formed the hard-coat layer on the polycarbonate film, and was set as Examples 2-9.
アクリロイルピペリジン：１-アクリロイルピペリジン
アクリロイルピロリジン：１-アクリロイルピロリジン
ＤＰＨＡ：ＫＡＹＡＲＡＤ ＤＰＨＡ：ジペンタエリスリトールヘキサアクリレート（日本化薬製）
Ｔ−１４２０：ＫＡＹＡＲＡＤ Ｔ−１４２０：ジペンタエリスリトールテトラアクリレート（日本化薬製）
Ｕ−１５ＨＡ：１５官能ウレタンアクリレート（新中村化学製）
ＬＲ−２４８：ポリメタクリル酸メチル系樹脂（三菱レイヨン製：重量平均分子量１５０，０００）
Ｍ−６６６４：ポリメタクリル酸ｉ−ブチル、ポリメタクリル酸ｎ−ブチル共重合系樹脂（根上工業製：重量平均分子量１８０，０００）
Ｉｒｇａｃｕｒｅ９０７：２−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（チバ・スペシャリティーケミカルズ製）
Ｉｒｇａｃｕｒｅ１８４：１−ヒドロキシ−シクロヘキシル−フェニル−ケトン（チバ・スペシャリティーケミカルズ製）
Acrylyl piperidine: 1-acryloyl piperidine acryloyl pyrrolidine: 1-acryloyl pyrrolidine DPHA: KAYARAD DPHA: dipentaerythritol hexaacrylate (manufactured by Nippon Kayaku)
T-1420: KAYARAD T-1420: Dipentaerythritol tetraacrylate (manufactured by Nippon Kayaku)
U-15HA: 15 functional urethane acrylate (manufactured by Shin-Nakamura Chemical)
LR-248: Polymethyl methacrylate resin (Mitsubishi Rayon: weight average molecular weight 150,000)
M-6664: poly (i-butyl methacrylate), poly (n-butyl methacrylate) copolymer resin (manufactured by Negami Kogyo: weight average molecular weight 180,000)
Irgacure 907: 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropan-1-one (manufactured by Ciba Specialty Chemicals)
Irgacure 184: 1-hydroxy-cyclohexyl-phenyl-ketone (Ciba Specialty Chemicals)
表２に示した通り、本発明における硬化性樹脂組成物を用いた実施例１〜９では、鉛筆硬度 Ｈ、テーバー摩耗試験におけるヘイズ値上昇も少なく、耐摩耗性、耐擦傷性に優れたハードコート層が形成された。また、実施例１〜９では、熱成形性にも優れた汎用性の高いハードコート層が形成された。 As shown in Table 2, in Examples 1 to 9 using the curable resin composition in the present invention, the pencil hardness H, the haze value increase in the Taber abrasion test is small, and the hardware excellent in abrasion resistance and scratch resistance. A coat layer was formed. In Examples 1 to 9, a highly versatile hard coat layer excellent in thermoformability was formed.
比較例１〜３として、１８０μｍのポリカーボネートフィルムにハードコート層が形成された市販のフィルム（三菱エンジニアリングプラスチックス製 ＭＲＧ０５、およびサビックイノベーティブプラスチックス製 ＨＰ−９２）、及び上記実施例で用いたポリカーボネートフィルム（レキサンＰＣ）の鉛筆硬度試験、テーバー磨耗試験、真空成形試験を行った。 As Comparative Examples 1 to 3, a commercially available film (MRG05 manufactured by Mitsubishi Engineering Plastics and HP-92 manufactured by Subic Innovative Plastics) in which a hard coat layer is formed on a polycarbonate film of 180 μm, and the polycarbonate used in the above examples The film (Lexan PC) was subjected to a pencil hardness test, a Taber abrasion test, and a vacuum forming test.
その結果表３に示したとおり、比較例１〜２は鉛筆硬度が高く、耐磨耗性に優れるが、真空成形時に絞り部分が２ｍｍ以上ある部位でクラックを生じ、真空成形を行うことができなかった。また、比較例３は、真空成形を行うことができるものの鉛筆硬度が４Ｂであり、テーバー磨耗性にも劣るものであった。 As a result, as shown in Table 3, Comparative Examples 1 and 2 have high pencil hardness and excellent wear resistance. However, when vacuum forming is performed, cracks are generated at a portion where the drawn portion is 2 mm or more, and vacuum forming can be performed. There wasn't. Moreover, although the comparative example 3 can perform vacuum forming, the pencil hardness is 4B and it was inferior to Taber abrasion property.
Claims (10)
アクリロイル化合物、多官能性アクリル酸エステルおよび熱可塑性樹脂の配合量を合計１００重量％とした時に、アクリロイル化合物を３０〜７０重量％、多官能性アクリル酸エステルを２０〜４０重量％、および熱可塑性樹脂を５〜３５重量％の範囲で含有することを特徴とする硬化性樹脂組成物。
30 to 70% by weight of the acryloyl compound, 20 to 40% by weight of the polyfunctional acrylate, and thermoplastic when the total amount of the acryloyl compound, the polyfunctional acrylate and the thermoplastic resin is 100% by weight A curable resin composition comprising a resin in a range of 5 to 35% by weight .
アクリロイル化合物、多官能性アクリル酸エステルおよび熱可塑性樹脂の配合量を合計１００重量％とした時に、アクリロイル化合物を３０〜７０重量％、多官能性アクリル酸エステルを２０〜４０重量％、および熱可塑性樹脂を５〜３５重量％の範囲で含有することを特徴とする硬化性樹脂組成物。
30 to 70% by weight of the acryloyl compound, 20 to 40% by weight of the polyfunctional acrylate, and thermoplastic when the total amount of the acryloyl compound, the polyfunctional acrylate and the thermoplastic resin is 100% by weight A curable resin composition comprising a resin in a range of 5 to 35% by weight .
Further comprising a reactive UV absorber, a curable resin composition according to any one of claims 1-9.
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