CN1255467C - Protective film composition for cylindrical shock insulator of liquid crystal display element - Google Patents
Protective film composition for cylindrical shock insulator of liquid crystal display element Download PDFInfo
- Publication number
- CN1255467C CN1255467C CN 02108748 CN02108748A CN1255467C CN 1255467 C CN1255467 C CN 1255467C CN 02108748 CN02108748 CN 02108748 CN 02108748 A CN02108748 A CN 02108748A CN 1255467 C CN1255467 C CN 1255467C
- Authority
- CN
- China
- Prior art keywords
- methyl
- acrylate
- liquid crystal
- crystal display
- protective film
- 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.)
- Expired - Lifetime
Links
- 239000000203 mixture Substances 0.000 title claims abstract description 77
- 239000004973 liquid crystal related substance Substances 0.000 title claims abstract description 32
- 230000001681 protective effect Effects 0.000 title claims description 47
- 239000012212 insulator Substances 0.000 title claims description 37
- 230000035939 shock Effects 0.000 title claims description 37
- 239000011347 resin Substances 0.000 claims abstract description 30
- 229920005989 resin Polymers 0.000 claims abstract description 30
- 239000000178 monomer Substances 0.000 claims abstract description 12
- -1 alkyl methyl vinylformic acid Chemical compound 0.000 claims description 37
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 claims description 20
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims description 16
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 15
- 230000014509 gene expression Effects 0.000 claims description 15
- 239000005977 Ethylene Substances 0.000 claims description 13
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 13
- 150000001875 compounds Chemical class 0.000 claims description 12
- 239000000126 substance Substances 0.000 claims description 12
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 claims description 11
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 11
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 10
- 229910000077 silane Inorganic materials 0.000 claims description 10
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 9
- 125000004432 carbon atom Chemical group C* 0.000 claims description 9
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 9
- 239000004925 Acrylic resin Substances 0.000 claims description 7
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 7
- UHESRSKEBRADOO-UHFFFAOYSA-N ethyl carbamate;prop-2-enoic acid Chemical compound OC(=O)C=C.CCOC(N)=O UHESRSKEBRADOO-UHFFFAOYSA-N 0.000 claims description 7
- 239000002904 solvent Substances 0.000 claims description 7
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 claims description 6
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 6
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 6
- 239000002253 acid Substances 0.000 claims description 6
- 150000002148 esters Chemical class 0.000 claims description 6
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 6
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 5
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 claims description 5
- 125000000217 alkyl group Chemical group 0.000 claims description 5
- 229920001971 elastomer Polymers 0.000 claims description 5
- 235000019439 ethyl acetate Nutrition 0.000 claims description 5
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 5
- ARXJGSRGQADJSQ-UHFFFAOYSA-N 1-methoxypropan-2-ol Chemical compound COCC(C)O ARXJGSRGQADJSQ-UHFFFAOYSA-N 0.000 claims description 4
- 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 4
- ZNQVEEAIQZEUHB-UHFFFAOYSA-N 2-ethoxyethanol Chemical compound CCOCCO ZNQVEEAIQZEUHB-UHFFFAOYSA-N 0.000 claims description 4
- YEJRWHAVMIAJKC-UHFFFAOYSA-N 4-Butyrolactone Chemical compound O=C1CCCO1 YEJRWHAVMIAJKC-UHFFFAOYSA-N 0.000 claims description 4
- KWOLFJPFCHCOCG-UHFFFAOYSA-N Acetophenone Chemical compound CC(=O)C1=CC=CC=C1 KWOLFJPFCHCOCG-UHFFFAOYSA-N 0.000 claims description 4
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical group C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 claims description 4
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 4
- NTIZESTWPVYFNL-UHFFFAOYSA-N Methyl isobutyl ketone Chemical compound CC(C)CC(C)=O NTIZESTWPVYFNL-UHFFFAOYSA-N 0.000 claims description 4
- UIHCLUNTQKBZGK-UHFFFAOYSA-N Methyl isobutyl ketone Natural products CCC(C)C(C)=O UIHCLUNTQKBZGK-UHFFFAOYSA-N 0.000 claims description 4
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims description 4
- 125000005250 alkyl acrylate group Chemical group 0.000 claims description 4
- 125000003700 epoxy group Chemical group 0.000 claims description 4
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 4
- 229940043265 methyl isobutyl ketone Drugs 0.000 claims description 4
- 229940059574 pentaerithrityl Drugs 0.000 claims description 4
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 claims description 4
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 claims description 4
- 239000002210 silicon-based material Substances 0.000 claims description 4
- 239000007983 Tris buffer Substances 0.000 claims description 3
- 150000001732 carboxylic acid derivatives Chemical class 0.000 claims description 3
- SHZIWNPUGXLXDT-UHFFFAOYSA-N ethyl hexanoate Chemical compound CCCCCC(=O)OCC SHZIWNPUGXLXDT-UHFFFAOYSA-N 0.000 claims description 3
- 125000002768 hydroxyalkyl group Chemical group 0.000 claims description 3
- JYEUMXHLPRZUAT-UHFFFAOYSA-N 1,2,3-triazine Chemical compound C1=CN=NN=C1 JYEUMXHLPRZUAT-UHFFFAOYSA-N 0.000 claims description 2
- FENFUOGYJVOCRY-UHFFFAOYSA-N 1-propoxypropan-2-ol Chemical compound CCCOCC(C)O FENFUOGYJVOCRY-UHFFFAOYSA-N 0.000 claims description 2
- CUDYYMUUJHLCGZ-UHFFFAOYSA-N 2-(2-methoxypropoxy)propan-1-ol Chemical compound COC(C)COC(C)CO CUDYYMUUJHLCGZ-UHFFFAOYSA-N 0.000 claims description 2
- XNWFRZJHXBZDAG-UHFFFAOYSA-N 2-METHOXYETHANOL Chemical compound COCCO XNWFRZJHXBZDAG-UHFFFAOYSA-N 0.000 claims description 2
- LDHQCZJRKDOVOX-UHFFFAOYSA-N 2-butenoic acid Chemical compound CC=CC(O)=O LDHQCZJRKDOVOX-UHFFFAOYSA-N 0.000 claims description 2
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 claims description 2
- MCKWYBMOGZCGFR-UHFFFAOYSA-N C(C1CO1)OCCCC(OOOC)C Chemical compound C(C1CO1)OCCCC(OOOC)C MCKWYBMOGZCGFR-UHFFFAOYSA-N 0.000 claims description 2
- NGMNTLCQDNNBNT-UHFFFAOYSA-N C(C=C)(=O)OC.C(CS)(=O)OCCOC(CS)=O Chemical compound C(C=C)(=O)OC.C(CS)(=O)OCCOC(CS)=O NGMNTLCQDNNBNT-UHFFFAOYSA-N 0.000 claims description 2
- 239000004215 Carbon black (E152) Substances 0.000 claims description 2
- 229920002943 EPDM rubber Polymers 0.000 claims description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 2
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 2
- 229920003171 Poly (ethylene oxide) Polymers 0.000 claims description 2
- NBBJYMSMWIIQGU-UHFFFAOYSA-N Propionic aldehyde Chemical compound CCC=O NBBJYMSMWIIQGU-UHFFFAOYSA-N 0.000 claims description 2
- 125000002947 alkylene group Chemical group 0.000 claims description 2
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 2
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 claims description 2
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 claims description 2
- 230000032050 esterification Effects 0.000 claims description 2
- 238000005886 esterification reaction Methods 0.000 claims description 2
- FKRCODPIKNYEAC-UHFFFAOYSA-N ethyl propionate Chemical compound CCOC(=O)CC FKRCODPIKNYEAC-UHFFFAOYSA-N 0.000 claims description 2
- 229930195733 hydrocarbon Natural products 0.000 claims description 2
- 150000002430 hydrocarbons Chemical class 0.000 claims description 2
- 229910052739 hydrogen Inorganic materials 0.000 claims description 2
- 239000001257 hydrogen Substances 0.000 claims description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 2
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 claims description 2
- LZCLXQDLBQLTDK-UHFFFAOYSA-N lactic acid ethyl ester Natural products CCOC(=O)C(C)O LZCLXQDLBQLTDK-UHFFFAOYSA-N 0.000 claims description 2
- 229920001228 polyisocyanate Polymers 0.000 claims description 2
- 239000005056 polyisocyanate Substances 0.000 claims description 2
- 229920001451 polypropylene glycol Polymers 0.000 claims description 2
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 claims 3
- UAEPNZWRGJTJPN-UHFFFAOYSA-N methylcyclohexane Chemical compound CC1CCCCC1 UAEPNZWRGJTJPN-UHFFFAOYSA-N 0.000 claims 2
- LCGLNKUTAGEVQW-UHFFFAOYSA-N Dimethyl ether Chemical compound COC LCGLNKUTAGEVQW-UHFFFAOYSA-N 0.000 claims 1
- XBDQKXXYIPTUBI-UHFFFAOYSA-N Propionic acid Chemical compound CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 claims 1
- 238000007334 copolymerization reaction Methods 0.000 claims 1
- XXJWXESWEXIICW-UHFFFAOYSA-N diethylene glycol monoethyl ether Chemical compound CCOCCOCCO XXJWXESWEXIICW-UHFFFAOYSA-N 0.000 claims 1
- 229940075557 diethylene glycol monoethyl ether Drugs 0.000 claims 1
- AANLSOCSNMYRRR-UHFFFAOYSA-N heptane;octane Chemical compound CCCCCCC.CCCCCCCC AANLSOCSNMYRRR-UHFFFAOYSA-N 0.000 claims 1
- GYNNXHKOJHMOHS-UHFFFAOYSA-N methyl-cycloheptane Natural products CC1CCCCCC1 GYNNXHKOJHMOHS-UHFFFAOYSA-N 0.000 claims 1
- 229920003051 synthetic elastomer Polymers 0.000 claims 1
- 239000004593 Epoxy Substances 0.000 abstract description 2
- 239000011230 binding agent Substances 0.000 abstract 3
- 125000006850 spacer group Chemical group 0.000 abstract 2
- 150000003377 silicon compounds Chemical class 0.000 abstract 1
- 239000012528 membrane Substances 0.000 description 20
- 230000000052 comparative effect Effects 0.000 description 18
- 238000000034 method Methods 0.000 description 9
- 239000002585 base Substances 0.000 description 6
- 239000011248 coating agent Substances 0.000 description 6
- 238000000576 coating method Methods 0.000 description 6
- 239000000758 substrate Substances 0.000 description 6
- 230000015572 biosynthetic process Effects 0.000 description 5
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 4
- 239000003795 chemical substances by application Substances 0.000 description 4
- 230000006835 compression Effects 0.000 description 4
- 238000007906 compression Methods 0.000 description 4
- 238000000354 decomposition reaction Methods 0.000 description 4
- 238000011084 recovery Methods 0.000 description 4
- 229910052710 silicon Inorganic materials 0.000 description 4
- 239000010703 silicon Substances 0.000 description 4
- JHPBZFOKBAGZBL-UHFFFAOYSA-N (3-hydroxy-2,2,4-trimethylpentyl) 2-methylprop-2-enoate Chemical compound CC(C)C(O)C(C)(C)COC(=O)C(C)=C JHPBZFOKBAGZBL-UHFFFAOYSA-N 0.000 description 3
- NIXOWILDQLNWCW-UHFFFAOYSA-N Acrylic acid Chemical compound OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 3
- 239000000470 constituent Substances 0.000 description 3
- 238000001914 filtration Methods 0.000 description 3
- 238000011835 investigation Methods 0.000 description 3
- 125000003866 trichloromethyl group Chemical group ClC(Cl)(Cl)* 0.000 description 3
- LELKUNFWANHDPG-UHFFFAOYSA-N 2-(oxiran-2-ylmethoxymethyl)oxirane;prop-2-enoic acid Chemical compound OC(=O)C=C.C1OC1COCC1CO1 LELKUNFWANHDPG-UHFFFAOYSA-N 0.000 description 2
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 2
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 2
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 230000000996 additive effect Effects 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- 150000008366 benzophenones Chemical class 0.000 description 2
- FFSAXUULYPJSKH-UHFFFAOYSA-N butyrophenone Chemical compound CCCC(=O)C1=CC=CC=C1 FFSAXUULYPJSKH-UHFFFAOYSA-N 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
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- PSGCQDPCAWOCSH-UHFFFAOYSA-N (4,7,7-trimethyl-3-bicyclo[2.2.1]heptanyl) prop-2-enoate Chemical compound C1CC2(C)C(OC(=O)C=C)CC1C2(C)C PSGCQDPCAWOCSH-UHFFFAOYSA-N 0.000 description 1
- XDHOEHJVXXTEDV-UHFFFAOYSA-N 1-ethoxyprop-1-ene Chemical group CCOC=CC XDHOEHJVXXTEDV-UHFFFAOYSA-N 0.000 description 1
- MNAHQWDCXOHBHK-UHFFFAOYSA-N 1-phenylpropane-1,1-diol Chemical compound CCC(O)(O)C1=CC=CC=C1 MNAHQWDCXOHBHK-UHFFFAOYSA-N 0.000 description 1
- UHFFVFAKEGKNAQ-UHFFFAOYSA-N 2-benzyl-2-(dimethylamino)-1-(4-morpholin-4-ylphenyl)butan-1-one Chemical compound C=1C=C(N2CCOCC2)C=CC=1C(=O)C(CC)(N(C)C)CC1=CC=CC=C1 UHFFVFAKEGKNAQ-UHFFFAOYSA-N 0.000 description 1
- DZZAHLOABNWIFA-UHFFFAOYSA-N 2-butoxy-1,2-diphenylethanone Chemical compound C=1C=CC=CC=1C(OCCCC)C(=O)C1=CC=CC=C1 DZZAHLOABNWIFA-UHFFFAOYSA-N 0.000 description 1
- XMLYCEVDHLAQEL-UHFFFAOYSA-N 2-hydroxy-2-methyl-1-phenylpropan-1-one Chemical compound CC(C)(O)C(=O)C1=CC=CC=C1 XMLYCEVDHLAQEL-UHFFFAOYSA-N 0.000 description 1
- ZXTHWIZHGLNEPG-UHFFFAOYSA-N 2-phenyl-4,5-dihydro-1,3-oxazole Chemical compound O1CCN=C1C1=CC=CC=C1 ZXTHWIZHGLNEPG-UHFFFAOYSA-N 0.000 description 1
- YHQXBTXEYZIYOV-UHFFFAOYSA-N 3-methylbut-1-ene Chemical compound CC(C)C=C YHQXBTXEYZIYOV-UHFFFAOYSA-N 0.000 description 1
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- WFMUVOBLVSSBBU-UHFFFAOYSA-N C(=O)C(Cl)(Cl)Cl.C(CCC)C1=CC=CC=C1 Chemical compound C(=O)C(Cl)(Cl)Cl.C(CCC)C1=CC=CC=C1 WFMUVOBLVSSBBU-UHFFFAOYSA-N 0.000 description 1
- OBMOYFIQFLLHMK-UHFFFAOYSA-N C1(CCCC1)C(=CC)OCC Chemical group C1(CCCC1)C(=CC)OCC OBMOYFIQFLLHMK-UHFFFAOYSA-N 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical group CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 1
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- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
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- 230000002950 deficient Effects 0.000 description 1
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- 238000012423 maintenance Methods 0.000 description 1
- YLHXLHGIAMFFBU-UHFFFAOYSA-N methyl phenylglyoxalate Chemical compound COC(=O)C(=O)C1=CC=CC=C1 YLHXLHGIAMFFBU-UHFFFAOYSA-N 0.000 description 1
- LUCXVPAZUDVVBT-UHFFFAOYSA-N methyl-[3-(2-methylphenoxy)-3-phenylpropyl]azanium;chloride Chemical compound Cl.C=1C=CC=CC=1C(CCNC)OC1=CC=CC=C1C LUCXVPAZUDVVBT-UHFFFAOYSA-N 0.000 description 1
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- 238000005496 tempering Methods 0.000 description 1
- 229920002725 thermoplastic elastomer Polymers 0.000 description 1
- DVKJHBMWWAPEIU-UHFFFAOYSA-N toluene 2,4-diisocyanate Chemical compound CC1=CC=C(N=C=O)C=C1N=C=O DVKJHBMWWAPEIU-UHFFFAOYSA-N 0.000 description 1
- LENZDBCJOHFCAS-UHFFFAOYSA-N tris Chemical compound OCC(N)(CO)CO LENZDBCJOHFCAS-UHFFFAOYSA-N 0.000 description 1
Abstract
The invention provides a resist composition for the column spacers of a liquid crystal display element. The resist composition contains 10-40 pts.wt. binder resin selected from the group comprising a binder resin of formula (1), a binder resin of formula (2) and a mixture of these, 1-20 pts.wt. polyfunctional monomer having an ethylenically unsaturated bond, 1-10 pts.wt. photoinitiator and 0.001-0.1 pt.wt. epoxy-containing silicon compound. The resist composition is excellent in heat resistance, can form a pattern in an appropriate thickness when the column spacers of a liquid crystal display element are formed and has good flatness and resolution, a good residual film rate and good pattern stability.
Description
Technical field
The present invention relates to the protective film composition for cylindrical shock insulator of liquid crystal display device; when particularly relating to the cylindrical shock insulator formation of liquid crystal display device; forming figure on suitable thickness, is the protective membrane composition of flatness, resolution, residual film ratio and figure excellent in stability.
Background technology
Generally, liquid crystal display device (LCD) is to be made of dottle pin and liquid crystal between 2 pieces of opposed upper and lower plates and the insertion plate, and dottle pin promptly plays the effect of protection as the cell gap of sheet separation to the thickness of liquid crystal layer.Has only the performance that keeps certain cell gap just can present the liquid crystal display device of high-speed responsive, high comparative, wide viewing angle etc.
Now, be that diameter group is a bit larger tham the transparent spherical or columned polymethylmethacrylate of cell gap or the method that the silicon particle disperses, applies as the most widely used dottle pin formation method.This method is owing to not only produce the phenomenon of spherical or cylindric particle partial coagulation when liquid crystal injects, and because liquid crystal board moves or because of vibration, impact and to cause that particle position moves and can not disperse uniformly, so the deviation in generation unit gap and be difficult to the cell gap that keeps certain.Thus, it is inhomogeneous to produce thickness of liquid crystal layer, makes the problem of liquid crystal display device foxy, figure deformation.In addition, on alignment films, produce scratch and can damage alignment films, pressing the possibility that electrode damage is also arranged when encapsulating at panel substrate up and down.These problems are because the The Enlargement Tendency of the liquid crystal display device of TFT LCD etc., or along with the information terminal of Cell phone, BB machine etc. or mobile model communication machine, vehicle further become deep problem with the exploitation of purposes such as haulage system, expansion.
As the method that addresses these problems, propose to utilize Photocurable composition to form the method for fixed cylindrical shock insulator.In Republic of Korea's publication communique 1999-88297 number, after disclosing the constituent that coating is made up of acrylate cross linked dose of multipolymer, polybasic and the light trigger of vinylformic acid and acrylate, irradiation ultraviolet radiation solidifies desired portion, washs the method that the method for removing uncured part forms dottle pin with alkali aqueous solution.This method is owing to forming the fixed dottle pin with certain thickness by certain interval, so can have nothing to do with outside atmosphere and the maintenance uniform cell gap.
, as disclosed Photocurable composition in the above-mentioned publication communique, be difficult to be formed on the thickness of 3～10 μ m of the suitable cell gap that uses in the liquid crystal indicator.That is: as above-mentioned composition, be difficult to the viscosity that reaches suitable when having the film of thickness of 3～10 μ m with the spin coating manufactured, so the operation that above-mentioned composition must be rotated repeatedly coating, solidify developing is so that form the dottle pin of suitable depth, this operation is very bothersome.In addition, above-mentioned composition solidifies the back volumetric shrinkage and is difficult to form the dottle pin with uniform thickness, so thermotolerance and figure stability are also poor because acrylic resin is used as principal constituent.
Summary of the invention
When the technical task that the present invention will solve is to be provided at the cylindrical shock insulator formation of liquid crystal display device, can form the suitable depth of figure, and the good protective membrane composition of thermotolerance, figure stability, flatness, resolution and residual film ratio.
In order to realize above-mentioned technical task; the invention provides the protective film composition for cylindrical shock insulator of liquid crystal display device, it is characterized in that containing useful following general formula 1 expression adhesion resin, form any one adhesion resin 10～40 weight parts, multi-functional monomer 1～20 weight part, light trigger 1～10 weight part that mass selection goes out and silicon based compound 0.001～0.1 weight part that contains epoxy group(ing) by the adhesion resin of following general formula 2 expressions and these mixtures with ethylene unsaturated bond.
General formula 1 is:
In above-mentioned general formula 1, X is hydrogen atom or methyl, Y
1Be the alkyl or the hydroxyalkyl of carbonatoms 2～16, Y
2Be any one that the compound of following chemical formula (I)～chemical formula (XX) expression is selected.
In above-mentioned chemical formula (I)～chemical formula (XX), R
1Be hydrogen atom or methyl, R
2Be alkylene group, the R of carbonatoms 1～10
3Be residual base, the R of the hydrocarbon of carbonatoms 1～10
4Be hydrogen or methyl, R
5Alkylene group, the k that is carbonatoms 1～10 is 0～10 integer.
General formula 2 is:
In above-mentioned general formula 2, polymerized unit A is by the benzyl methacrylic ester, vinylbenzene, alpha-methyl styrene, iso-bornyl acrylate and isobornyl methacrylic ester, two cyclopentyl acrylate, two cyclopentyl-methyl acrylate, the dicyclopentenyl acrylate, the dicyclopentenyl methacrylic ester, two cyclopentyl ethoxy propylene acid esters, two cyclopentyl ethoxyl methyl acrylate, dicyclopentenyl ethoxy propylene acid esters, dicyclopentenyl ethoxyl methyl acrylate is formed any one that mass selection goes out, B is acrylic or methacrylic acid, C is by glycidyl methacrylate, the hydroxyethyl methacrylic ester, the dimethylamino methyl acrylate, acrylamide is formed any one that mass selection goes out, and the adhesion resin of above-mentioned general formula 2 is not to be subjected to polymerized unit A, the random copolymers of the assortment sequence limit of B and C.
The adhesion resin of representing with above-mentioned general formula 1 is to contain the monomer of carboxylic acid and have the polymer of monomers of two keys, if coating contains when forming figure behind the composition of the present invention of such multipolymer, then do not have the defective of residue etc. behind the developing, the planarization rate is very good.That is the Y of above-mentioned general formula 1,
1Be alkyl or hydroxyalkyl, can improve bounding force, and at Y with carbon atom of 2～16
2On to contain adhesion resin in the past that the acrylic copolymer resin of aromatic series base forms different and contain the alicyclic structure that expands, so not only improve residual film ratio, and because vitrifying tansition temperature height, so thermotolerance is also good.
Use is by the molecular-weight average of the adhesion resin of above-mentioned general formula 1 expression preferably 2,000～50,000, dispersity is 1.0～5.0, acidity is 30～400KOHmg/g, the preferred molecular-weight average that is to use is 5,000～40,000, dispersity is 1.6～3.0, acidity is 50～150KOHmg/g.
About equally effect during the adhesion resin that also shown when in addition, using adhesion resin by above-mentioned general formula 2 expressions and used by above-mentioned general formula 1 expression.In adhesion resin, in the scope that does not hinder the object of the invention, can import the polymerized unit of other kinds, for example and then import the alkyl acrylate or the alkylmethacrylate of the such alkyl several 2～16 of the D of following general formula 3 by 2 expressions of above-mentioned general formula.As such repeating unit, more specifically can enumerate methacrylic ester, butyl methyl acrylate, lauryl methyl acrylate, methacrylic ester, butylacrylic acid ester, lauryl acrylate, vinylbenzene etc.
General formula 3 is:
By the molecular-weight average of the adhesion resin of above-mentioned general formula 2 expressions preferably 2,000～100,000, dispersity is 1.0～5.0, acidity is 30～400KOHmg/g, and more preferably molecular-weight average is 5,000～60,000, dispersity is 1.6～3.0, acidity is 50～150KOHmg/g.
Particularly, if in the time of will using by the adhesion resin of above-mentioned general formula 1 expression with by the adhesion resin mixing of general formula 2 expressions, the multi-functional monomer in the composition and the intermiscibility increase of adhesion resin can improve the tack with glass surface, and the splitting resistance and the albinism that not only improve figure also disappear.
Cylindrical shock insulator at liquid crystal display device of the present invention is used in the protectiveness constituent, and then can add elastomerics 1～20 weight part with ethylene unsaturated bond.As such elastomerics, the ethylene unsaturated bond number that preferably uses side chain is 2～15 material, for example can use the urethane acrylate resin that has ethylene unsaturated bond at side chain.As such urethane acrylate resin, have Japan new in the U series, UA series etc. of village community.In addition, as spendable elastomerics, modifications such as SBS, S1S, S1BS, EPDM, EP rubber, divinyl rubber, isopentene rubber are arranged thermoplastic elastomer etc., can be separately or mix more than 2 kinds and use with these materials.Added the cylindrical shock insulator of elastomeric protective membrane composition formation with such ethylene unsaturated bond; owing to make elasticity carry very highly; so can get rid of after forming screen board owing to be added to the pressure of plate, the possibility that bottom protective membrane or black matix, pseudo-colour filtering film unit etc. are cracked from the outside.
Functional monomer as ethylene unsaturated bond with the protective film composition for cylindrical shock insulator that is contained in liquid crystal display device of the present invention; can use the polymerizable compound that has at the employed ethene unsaturated link(age) of common photosensitive composite; for example can use ethylene glycol bisthioglycolate (methyl) acrylate; the ethyleneoxy group number is 2～14 polyoxyethylene glycol two (methyl) acrylate; TriMethylolPropane(TMP) two (methyl) acrylate; trimethylolpropane tris (methyl) acrylate; tetramethylolmethane three (methyl) acrylate; tetramethylolmethane four (methyl) acrylate; polypropylene glycol two (methyl) acrylate of propylidene oxygen radix 2～14; Dipentaerythritol five (methyl) acrylate; the polyvalent alcohol and the α of Dipentaerythritol six (methyl) acrylate etc., beta-unsaturated carboxylic acid carry out esterification and the compound that obtains and; at trimethylolpropane tris glycidyl ether vinylformic acid affixture; the containing (methyl) vinylformic acid of addition in the glycidyl compound of dihydroxyphenyl propane diglycidyl ether vinylformic acid affixture etc. and the compound that obtains and; the Bisphthalate of beta-hydroxyethyl (methyl) acrylate; the compound with hydroxyl and ethene unsaturated link(age) of the tolylene diisocyanate affixture of beta-hydroxyethyl (methyl) acrylate etc. and the ester cpds of polycarboxylic acid or with the affixture of polymeric polyisocyanate and; methyl (methyl) acrylate; ethyl (methyl) acrylate; butyl (methyl) acrylate; (methyl) alkyl acrylates of 2-ethylhexyl (methyl) acrylate etc. etc. mix use more than 2 kinds separately or in these.
Like this, the composition that will have the multi-functional monomer of the polymerizable compound of ethylene unsaturated bond, the elastomerics with ethylene unsaturated bond and an adhesion resin by the present invention is regulated aptly and can be made the protective film composition for cylindrical shock insulator that keeps elasticity, high heat resistance, high transparent, high planarization rate and figure stability.
In addition,,, make its dosage become minimum, preferably use is mixed separately or with them in methyl phenyl ketone system and benzophenone series in order to improve the transparency as the light trigger that contains protective membrane composition of the present invention.If the coloured words of light trigger itself just play a part to make the transparency to reduce, so as long as use the wavelength band when exposure to have suitable sensitivity, colourless light trigger just can be realized high transparent.Generally, in the crosslinking reaction of using the acrylic acid series multifunctional monomer, light trigger will use matchingly with the ultraviolet wavelength that uses, but as the mercuryvapour lamp of the most widely used ultraviolet wavelength owing to have the wavelength in 310～420nm zone, so preferably use the light trigger that can produce free radical in this wavelength region may.
As such light trigger; lrgacure369 is arranged; lrgacure907; the benzophenone series and the triazine of EPD/BMS mixed stockers etc. are light trigger; benzophenone is for example arranged; phenyl biphenyl ketone; 1-hydroxyl-1-benzoyl hexanaphthene; dibenzoyl; benzyl dimethyl ketal; 1-benzyl-1-dimethylamino-1-(4-morpholino benzoyl) propane; 2-morpholinyl-2-(4-methyl mercapto) benzoyl propane; thiophene oxane ketone; 1-chloro-4-propoxy-thiophene oxane ketone; sec.-propyl thiophene oxane ketone; diethyl thiophene oxane ketone; EAQ; 4-benzoyl-4-methyldiphenyl base sulphur; the benzoin butyl ether; 2-hydroxyl-2-benzoyl propane; 2-hydroxyl-2-(4-sec.-propyl) benzoyl propane; 4-butylbenzene formyl trichloromethane; 4-phenoxy benzonitrile acyl methylene dichloride; methyl benzoylformate; 1; two (9-acridyl) heptane of 7-; 9-n-butyl-3; 6-two (2-morpholino isobutyryl) card azoles; 2-methyl-4; two (the trichloromethyl)-S-triazines of 6-; 2-phenyl-4; two (the trichloromethyl)-S-triazines of 6-; 2-naphthyl-4, two (the trichloromethyl)-S-triazines of 6-etc.
The silicon with epoxy group(ing) that is contained in protective membrane composition of the present invention is additive, the cohesive force of ITO electrode and composition improve to be solidified after, improved heat-resistant quality.As such silicon based compound, (3-glycidoxypropyl) trimethoxy (oxyethyl group) silane, (3-glycidoxypropyl) methyl dimethoxy oxygen base (oxyethyl group) silane, (3-glycidoxypropyl) dimethyl methoxy base (oxyethyl group) silane, 3 are arranged, 4-epoxy group(ing) butyl trimethoxy (oxyethyl group) silane, 2-(3,4-epoxy group(ing) cyclohexyl) ethyl trimethoxy (oxyethyl group) silane etc. can be used alone or as a mixture them respectively.
In addition, in protective film composition for cylindrical shock insulator of the present invention, can add the additive that intermiscibility is arranged of light increase and decrease agent, hot stopper, defoamer, leveling agent etc. as required.
Protective film composition for cylindrical shock insulator of the present invention; be after adding solvent after spin coated on the substrate; use the mask irradiation ultraviolet radiation and adopt the method for developing in the alkali developer to form cylindrical shock insulator; the interpolation solvent in 10～35cps scope, is preferably made viscosity adjustment cell gap is remained on the thick coating of 3～10 μ m.And then preferably regulate viscosity to 15～30cps, and after coating, there is not the pore of film, film thickness is more favourable for regulating.As such solvent, except the coating of composition, consider to obtain the transparency of film, with adhesion resin, during the intermiscibility of multifunctional monomer and compound thereof, can be used alone or as a mixture more than a kind from the following solvent of selecting, i.e. ethylhexoate, the butylacetic acid ester, diethylene glycol dimethyl ether, glycol ether dimethyl ethyl ether, methyl methoxy base propionic ester, ethyl ethoxy-c acid esters (EEP), the Solactol ester, methyl proxitol acetate (PGMEA), methyl proxitol, the propylene glycol propyl ether, methyl glycol ether acetic ester, ethyl glycol ether acetic ester, glycol ether methyl (or ethyl) acetic ester, acetone, methyl iso-butyl ketone (MIBK), pimelinketone, dimethyl formamide (DMF), N, N-N,N-DIMETHYLACETAMIDE (DMAc), N-N-methyl-2-2-pyrrolidone N-(NMP), gamma-butyrolactone, ether, ethylene glycol dimethyl ether, glyme, tetrahydrofuran (THF) (THF), methyl alcohol, ethanol, propyl alcohol, Virahol, methyl (or ethyl) cellosolve, glycol ether methyl (or ethyl) ether, the dipropylene glycol methyl ether, toluene, dimethylbenzene, hexane, heptane, octane.
Embodiment
Below, the present invention enumerates embodiment and comparative example explains in order to specifically describe., embodiments of the invention may be deformed to multiple other forms, and scope of the present invention is not subjected to restriction and the explanation of embodiment described later.Embodiments of the invention provide in order to make those skilled in the art further understand the present invention.
Embodiment 1
In the reaction tempering tank that ultraviolet ray cuts off film and stirrer is set according to described composition of following table 1 and content; add adhesion resin, multi-functional monomer, light trigger, silane successively and be epoxy compounds and fixed light increase and decrease agent, hot stopper, defoamer, leveling agent and produce protective film composition for cylindrical shock insulator after, stir at normal temperatures.Then, in composition, add solvent the viscosity adjustment of protective membrane composition is become 25cps.
Among the embodiment, (in general formula 1, X is methyl, Y to the above-mentioned general formula 1 of adhesion resin
1Be ethyl) Y
2Represent chemical formula (I)～chemical formula (XX) respectively with chemical formula (1-I)～chemical formula (1-XX), at this moment, R
1, R
2, R
3, R
4Be respectively methyl, methyl, ethyl and methyl, k is 1.
Embodiment 2～32
Except the composition according to the record of following table 1 changes the composition and content of composition of the foregoing description 1, make protective film composition for cylindrical shock insulator with Same Way.
Comparative example 1～8
Except using adhesion resin (molecular-weight average 30 by following general formula 4 expressions; 000) replaces the adhesion resin of the foregoing description 1; and the composition of putting down in writing according to following table 1 to make protective film composition for cylindrical shock insulator with Same Way outside the composition and content of changed composition.
General formula 4 is:
In above-mentioned general formula 4, p is 0.3, q is 0.2, r is 0.5.
Table 1
Embodiment 33～51
Except in the composition of the foregoing description 1 and then add the urethane acrylate resin, change outside composition and the content according to the composition of following table 2 record, make protective film composition for cylindrical shock insulator with Same Way.In table 2, represent that with UA1～UA15 the unsaturated double-bond number of the side chain of urethane acrylate resin (village community's goods during Japan is new) is 1～15 respectively.
Comparative example 9～13
Except using the adhesion resin of representing by the general formula 4 of comparative example 1～8 to replace the adhesion resin of the foregoing description 33～51; and the composition of putting down in writing according to following table 2 to make protective film composition for cylindrical shock insulator with Same Way outside the composition and content of changed composition.
Table 2
The evaluation of the above embodiment and the protective membrane composition of comparative example is carried out on the substrate of silicon chip or sheet glass etc., has carried out the performance evaluation of the thermal property investigation, flatness, residual film ratio, figure formation etc. of protective membrane composition.Particularly, further estimated the compression recovery rate of the composition that contains the urethane acrylate resin, its result is shown in following table 3 and table 4.
(1) thermal property investigation
In order to estimate the thermal properties of protective film composition for cylindrical shock insulator, use thermogravimetric analysis machine (Thermo gravimetric analysis:TGA) to measure heat decomposition temperature, 5% the temperature that reduces initial stage weight is compared as the initial stage decomposition temperature.
(2) flatness
Use the spin coated machine with the speed of 600rpm the protective membrane composition to be coated in substrate after last 13 second, pre-roast is 3 minutes under 90 ℃,, carries out the back roast and formed protective membrane in 30 seconds under 220 ℃ after 15 seconds with 365nm curing.The protective membrane that the used thickness tester will be formed on silicon chip or sheet glass is measured its thickness at 25 different places and is obtained the poor of maximum ga(u)ge and minimum thickness.
(3) residual film ratio
The protective film composition for cylindrical shock insulator spin coated on substrate, is measured and to be carried out the thickness behind the pre-roast and carry out the back roast and remove the ratio (%) of the thickness of the film that the back of desolvating forms.
(4) figure forms
The silicon chip that has formed the protective membrane figure is cut off from the vertical direction of line graph, shown the result who uses electron microscope observation from the section direction of figure.With pattern side wall is upright with the angle more than 80 ° for substrate, film is unbated is judged to be " well ", see that film reduces then be judged to be " film minimizing ".
(5) investigation of compression recovery rate
In order to estimate the compression recovery rate of protective film composition for cylindrical shock insulator, the sub-II of super pressure-sizing (Nanoindonter II) that makes of the MTS company of the U.S. is pressed into (Nanoindentation) experiment.Pressure uses dull and stereotyped perforation chip (Flat punch tip), after the load of adding 10mN stops 5 seconds, load is reduced to relatively restorative distance of 0.98mN.
Table 3
| Example | The initial stage decomposition temperature (℃) | Flatness (_) | Residual film ratio (%) | Graphics shape |
| Embodiment 1 | 254 | 350 | 90 | Well |
| Embodiment 2 | 253 | 321 | 90 | Well |
| Embodiment 3 | 253 | 331 | 90 | Well |
| Embodiment 4 | 253 | 351 | 90 | Well |
| Embodiment 5 | 255 | 367 | 90 | Well |
| Embodiment 6 | 254 | 369 | 90 | Well |
| Embodiment 7 | 250 | 384 | 90 | Well |
| Embodiment 8 | 245 | 374 | 90 | Well |
| Embodiment 9 | 255 | 389 | 90 | Well |
| Embodiment 10 | 253 | 390 | 90 | Well |
| Embodiment 11 | 252 | 387 | 90 | Well |
| Embodiment 12 | 250 | 391 | 90 | Well |
| Embodiment 13 | 248 | 400 | 90 | Well |
| Embodiment 14 | 246 | 418 | 90 | Well |
| Embodiment 15 | 247 | 397 | 90 | Well |
| Embodiment 16 | 250 | 405 | 90 | Well |
| Comparative example 1 | 228 | 2548 | 84 | Film reduces |
| Comparative example 2 | 225 | 2145 | 85 | Film reduces |
| Comparative example 3 | 220 | 2367 | 84 | Film reduces |
| Comparative example 4 | 217 | 2419 | 83 | Film reduces |
| Embodiment 17 | 256 | 325 | 90 | Well |
| Embodiment 18 | 253 | 304 | 90 | Well |
| Embodiment 19 | 254 | 313 | 90 | Well |
| Embodiment 20 | 252 | 332 | 90 | Well |
| Embodiment 21 | 254 | 343 | 90 | Well |
| Embodiment 22 | 253 | 346 | 90 | Well |
| Embodiment 23 | 252 | 362 | 90 | Well |
| Embodiment 24 | 250 | 351 | 90 | Well |
| Embodiment 25 | 251 | 369 | 90 | Well |
| Embodiment 26 | 249 | 373 | 90 | Well |
| Embodiment 27 | 251 | 369 | 90 | Well |
| Embodiment 28 | 253 | 372 | 90 | Well |
| Embodiment 29 | 247 | 380 | 90 | Well |
| Embodiment 30 | 249 | 395 | 90 | Well |
| Embodiment 31 | 245 | 375 | 90 | Well |
| Embodiment 32 | 248 | 384 | 90 | Well |
| Comparative example 5 | 218 | 2228 | 82 | Film reduces |
| Comparative example 6 | 215 | 2641 | 84 | Film reduces |
| Comparative example 7 | 220 | 2003 | 85 | Film reduces |
| Comparative example 8 | 217 | 2569 | 84 | Film reduces |
Table 4
| Example | Compression recovery rate (%) | The initial stage decomposition temperature (℃) | Flatness (_) | Residual film ratio (%) | Graphics shape |
| Embodiment 33 | 83 | 250 | 320 | 90 | Well |
| Embodiment 34 | 82 | 253 | 321 | 90 | Well |
| Embodiment 35 | 83 | 251 | 369 | 90 | Well |
| Embodiment 36 | 84 | 249 | 374 | 90 | Well |
| Embodiment 37 | 80 | 253 | 331 | 90 | Well |
| Embodiment 38 | 81 | 255 | 319 | 90 | Well |
| Embodiment 39 | 80 | 246 | 317 | 90 | Well |
| Embodiment 40 | 83 | 249 | 330 | 90 | Well |
| Embodiment 41 | 84 | 251 | 351 | 90 | Well |
| Embodiment 42 | 82 | 252 | 367 | 90 | Well |
| Embodiment 43 | 81 | 255 | 335 | 90 | Well |
| Embodiment 44 | 82 | 253 | 300 | 90 | Well |
| Embodiment 45 | 83 | 254 | 315 | 90 | Well |
| Embodiment 46 | 83 | 256 | 326 | 90 | Well |
| Embodiment 47 | 84 | 255 | 341 | 90 | Well |
| Embodiment 48 | 83 | 258 | 335 | 90 | Well |
| Embodiment 49 | 83 | 256 | 317 | 90 | Well |
| Embodiment 50 | 82 | 255 | 320 | 90 | Well |
| Embodiment 51 | 84 | 253 | 315 | 90 | Well |
| Comparative example 9 | 59 | 215 | 511 | 80 | Film reduces |
| Comparative example 10 | 62 | 213 | 498 | 80 | Film reduces |
| Comparative example 11 | 66 | 210 | 489 | 80 | Film reduces |
| Comparative example 12 | 60 | 208 | 525 | 80 | Film reduces |
From above-mentioned table 3 and table 4 as can be known, protective film composition for cylindrical shock insulator of the present invention is different with protective membrane composition in the past, excellent heat resistance not only, and residual film ratio, flatness and figure stability are also very good when forming film.Particularly; adopted the display element of the cylindrical shock insulator that the protective membrane composition by the elastomeric embodiment 33～51 with ethylene unsaturated bond that contains the urethane acrylate resene constituted; because its elasticity increases greatly; do not exist owing to be added to the pressure of screen board from the outside, and make bottom protective membrane or disruptive danger such as black matix, pseudo-colour filtering unit.
More than, above-mentioned protective membrane composition of the present invention, not only excellent heat resistance can evenly form figure, resolution, residual film ratio and figure excellent in stability on the suitable thickness.Therefore, if use protective membrane composition of the present invention to form cylindrical shock insulator, just can be irrelevant with the size of display element, keep uniform cell gap, can prevent the variation of moving or vibrate, impact the cell gap that causes owing to liquid crystal board.Particularly; the elasticity of the cylindrical shock insulator that is made of the elastomeric protective membrane composition that contains tool ethene unsaturated link(age) is very good; so adopted the liquid crystal display device of this cylindrical shock insulator; do not exist owing to be added to the pressure of screen board from the outside, and make bottom protective membrane or disruptive danger such as black matix, pseudo-colour filtering unit.
Claims (10)
1, the protective film composition for cylindrical shock insulator of liquid crystal display device; silicon based compound 0.001～0.1 weight part that it is characterized in that containing adhesion resin 10～40 weight parts, multi-functional monomer 1～20 weight part, light trigger 1～10 weight part of useful following general formula 1 expression and contain epoxy group(ing) with ethylene unsaturated bond
General formula 1 is:
In above-mentioned general formula 1, X is hydrogen atom or methyl, Y
1Be the alkyl or the hydroxyalkyl of carbonatoms 2～16, Y
2Be any one that the compound of following chemical formula (I)～chemical formula (XX) expression is selected,
In above-mentioned chemical formula (I)～chemical formula (XX), R
1Be hydrogen atom or methyl, R
2Be alkylene group, the R of carbonatoms 1～10
3Be residue, the R of the hydrocarbon of carbonatoms 1～10
4Be hydrogen or methyl, R
5Alkylene group, the k that is carbonatoms 1～10 is 0～10 integer.
2, the protective film composition for cylindrical shock insulator of liquid crystal display device according to claim 1; it is characterized in that the molecular-weight average by the adhesion resin of above-mentioned general formula 1 expression is 5; 000～40,000, dispersity is 1.6～3.0, acidity is 50～150KOHmg/g.
3, the protective film composition for cylindrical shock insulator of liquid crystal display device according to claim 1; it is characterized in that being 5 by the molecular-weight average of the adhesion resin of above-mentioned general formula 2 expressions; 000～60,000, dispersity is 1.6～3.0, acidity is 50～150KOHmg/g.
4, the protective film composition for cylindrical shock insulator of liquid crystal display device according to claim 1; it is characterized in that the resin of binding property that above-mentioned general formula 2 is represented, is that the alkyl number is 2～16 alkyl acrylate or alkyl methyl vinylformic acid and then copolymerization as polymerized unit.
5; the protective film composition for cylindrical shock insulator of liquid crystal display device according to claim 1; the functional monomer who it is characterized in that having above-mentioned ethylene unsaturated bond is more than one that go out from following composition mass selection: by ethylene glycol bisthioglycolate (methyl) acrylate; the ethyleneoxy group number is 2～14 polyoxyethylene glycol two (methyl) acrylate; TriMethylolPropane(TMP) two (methyl) acrylate; trimethylolpropane tris (methyl) acrylate; tetramethylolmethane three (methyl) acrylate; tetramethylolmethane four (methyl) acrylate; propylidene oxygen radix is 2～14 polypropylene glycol two (methyl) acrylate; Dipentaerythritol five (methyl) acrylate; Dipentaerythritol six (methyl) acrylate is formed polyvalent alcohol and the α that mass selection goes out, beta-unsaturated carboxylic acid carry out esterification and the compound that obtains and; (methyl) vinylformic acid of addition in containing glycidyl compound and the compound that obtains and; have the compound of hydroxyl and ethylene unsaturated bond and polycarboxylic acid ester cpds or with the affixture of polymeric polyisocyanate and; (methyl) alkyl acrylate.
6, the protective film composition for cylindrical shock insulator of liquid crystal display device according to claim 1 is characterized in that above-mentioned light trigger is to contain methyl phenyl ketone system or triazine is a light trigger.
7, the protective film composition for cylindrical shock insulator of liquid crystal display device according to claim 1; it is characterized in that the above-mentioned silicon based compound that contains epoxy group(ing) is from by (3-glycidoxypropyl) trimethoxy (oxyethyl group) silane, (3-glycidoxypropyl) methyl dimethoxy oxygen base (oxyethyl group) silane, (3-glycidoxypropyl) dimethyl methoxy base (oxyethyl group) silane, 3; one of selecting in groups of 4-epoxy group(ing) butyl trimethoxy (oxyethyl group) silane and 2-(3,4-epoxy group(ing) cyclohexyl) ethyl trimethoxy (oxyethyl group) silane groups.
8, the protective film composition for cylindrical shock insulator of liquid crystal display device according to claim 1, it is characterized in that so that add solvent with viscosity adjustment in 10～35cps scope.
9; the protective film composition for cylindrical shock insulator of liquid crystal display device according to claim 8; it is characterized in that solvent be from following composition mass selection go out a kind of, that is: ethylhexoate; the butylacetic acid ester; methyl methoxy base propionic ester; ethyl ethoxy-c acid esters; the Solactol ester; methyl proxitol acetate; methyl proxitol; the propylene glycol propyl ether; methyl glycol ether acetic ester; ethyl glycol ether acetic ester; glycol ether methyl acetic acid ester; the glycol ether ethylhexoate; acetone; methyl iso-butyl ketone (MIBK); pimelinketone; dimethyl formamide; N; the N-N,N-DIMETHYLACETAMIDE; the N-N-methyl-2-2-pyrrolidone N-; gamma-butyrolactone; ether; ethylene glycol dimethyl ether; glyme; tetrahydrofuran (THF); methyl alcohol; ethanol; propyl alcohol; Virahol; methylcyclohexane; ethyl cellosolve; the glycol ether methyl ether; diethylene glycol monoethyl ether; the dipropylene glycol methyl ether; toluene; dimethylbenzene; hexane; heptane; octane.
10, the protective film composition for cylindrical shock insulator of liquid crystal display device according to claim 1 is characterized in that and then add at least a elastomerics that is selected from the following group of 1～20 weight part: the urethane acrylate resin that has 2～15 ethylene unsaturated bonds on SBS, SIS, SIBS, EPDM, EP rubber, divinyl rubber, synthetic polyisoprene and the side chain.
Applications Claiming Priority (4)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| KR200117151 | 2001-03-31 | ||
| KR10-2001-0017151A KR100463309B1 (en) | 2001-03-31 | 2001-03-31 | Resist Composition For Column Spacer of LCD |
| KR1020020011196A KR100592418B1 (en) | 2002-03-02 | 2002-03-02 | Resist composition for liquid crystal display device column spacer |
| KR200211196 | 2002-03-02 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1379060A CN1379060A (en) | 2002-11-13 |
| CN1255467C true CN1255467C (en) | 2006-05-10 |
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Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 02108748 Expired - Lifetime CN1255467C (en) | 2001-03-31 | 2002-03-29 | Protective film composition for cylindrical shock insulator of liquid crystal display element |
Country Status (3)
| Country | Link |
|---|---|
| JP (1) | JP3467488B2 (en) |
| CN (1) | CN1255467C (en) |
| TW (1) | TWI266146B (en) |
Families Citing this family (22)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR101101660B1 (en) | 2003-03-24 | 2011-12-30 | 다이니폰 인사츠 가부시키가이샤 | Curable Resin Composition, Photosensitive Pattern-Forming Curable Resin Composition, Color Filter, Substrate For Liquid Crystalline Panel, and Liquid Crystalline Panel |
| JP4555940B2 (en) * | 2003-09-30 | 2010-10-06 | 日立化成工業株式会社 | Photosensitive resin composition for liquid crystal spacer and photosensitive element |
| JP4539066B2 (en) * | 2003-09-30 | 2010-09-08 | 日立化成工業株式会社 | Photosensitive resin composition for liquid crystal spacer and photosensitive element |
| KR100935569B1 (en) | 2004-02-20 | 2010-01-07 | 도오꾜오까고오교 가부시끼가이샤 | A compound containing an acid dissociable, dissolution inhibiting group containing a cycloaliphatic group |
| JP2006096965A (en) | 2004-02-20 | 2006-04-13 | Tokyo Ohka Kogyo Co Ltd | Polymer compound, photoresist composition containing such polymer compound, and method for forming resist pattern |
| JP5461472B2 (en) * | 2004-02-20 | 2014-04-02 | 東京応化工業株式会社 | POLYMER COMPOUND, PHOTORESIST COMPOSITION CONTAINING THE POLYMER COMPOUND, AND METHOD FOR FORMING RESIST PATTERN |
| WO2005101124A1 (en) * | 2004-04-08 | 2005-10-27 | Jsr Corporation | Radiation-sensitive resin composition, interlayer insulation film, microlens and process for producing them |
| TWI386714B (en) * | 2004-05-06 | 2013-02-21 | Dongjin Semichem Co Ltd | An interlayer organic insulating film for tft-lcd, acrylic copolymer resin used for an interlayer organic insulating film for tft-lcd and the preparation method thereof |
| JP4599484B2 (en) * | 2004-05-31 | 2010-12-15 | 凸版印刷株式会社 | Curable resin composition and color filter having photospacer formed using the same |
| JP4864375B2 (en) * | 2004-08-09 | 2012-02-01 | ドンジン セミケム カンパニー リミテッド | Photosensitive resin composition for spacer, spacer and liquid crystal display element |
| CN1757670B (en) * | 2004-10-07 | 2011-07-06 | Jsr株式会社 | Radial sensitive resin composite, microlens and manufacturing method therof and liquid crystal display element |
| JP4702594B2 (en) * | 2004-12-21 | 2011-06-15 | Ｄｉｃ株式会社 | Photocurable composition for liquid crystal panel seal and liquid crystal panel |
| CN1976961B (en) * | 2005-01-25 | 2010-05-19 | Lg化学株式会社 | Thermally curable resin composition with extended storage stability and good adhesive property |
| JP4934353B2 (en) * | 2005-06-10 | 2012-05-16 | ドンジン セミケム カンパニー リミテッド | Negative photosensitive resin composition |
| ATE538145T1 (en) * | 2005-09-26 | 2012-01-15 | Dejima Tech Bv | UV-CROSS-LINKABLE URETHANE (METH)ACRYLATE POLYMERS |
| KR20070039398A (en) | 2005-10-07 | 2007-04-11 | 히다치 막셀 가부시키가이샤 | Semiconductor device, semiconductor module and semiconductor module method for producing |
| WO2008140018A1 (en) * | 2007-05-11 | 2008-11-20 | Sekisui Chemical Co., Ltd. | Curable resin composition for column spacer, column spacer, and liquid-crystal display element |
| KR102060012B1 (en) | 2013-02-15 | 2019-12-30 | 삼성디스플레이 주식회사 | Photosensitive resin composition and method of forming pattern using the same |
| CN105392770A (en) * | 2013-06-21 | 2016-03-09 | 株式会社大赛璐 | Polyfunctional (meth)acrylate, and method for producing same |
| CN104793405B (en) * | 2015-04-28 | 2018-06-19 | 深圳市华星光电技术有限公司 | Liquid crystal display and liquid crystal display panel |
| CN104950527A (en) | 2015-07-01 | 2015-09-30 | 合肥鑫晟光电科技有限公司 | Display substrate, manufacturing method thereof, display panel and display device |
| US10747046B2 (en) | 2015-07-01 | 2020-08-18 | Boe Technology Group Co., Ltd. | Display substrate, display panel and display apparatus having the same, and fabricating method thereof |
-
2002
- 2002-03-29 JP JP2002097720A patent/JP3467488B2/en not_active Expired - Lifetime
- 2002-03-29 TW TW91106401A patent/TWI266146B/en not_active IP Right Cessation
- 2002-03-29 CN CN 02108748 patent/CN1255467C/en not_active Expired - Lifetime
Also Published As
| Publication number | Publication date |
|---|---|
| TWI266146B (en) | 2006-11-11 |
| JP2003021839A (en) | 2003-01-24 |
| CN1379060A (en) | 2002-11-13 |
| JP3467488B2 (en) | 2003-11-17 |
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