JPS63122745A - Partially crosslinked vinylidene halide based copolymer resin composition - Google Patents
Partially crosslinked vinylidene halide based copolymer resin compositionInfo
- Publication number
- JPS63122745A JPS63122745A JP26933086A JP26933086A JPS63122745A JP S63122745 A JPS63122745 A JP S63122745A JP 26933086 A JP26933086 A JP 26933086A JP 26933086 A JP26933086 A JP 26933086A JP S63122745 A JPS63122745 A JP S63122745A
- Authority
- JP
- Japan
- Prior art keywords
- mol
- resin composition
- formulas
- formula
- copolymer 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.)
- Granted
Links
- 239000011342 resin composition Substances 0.000 title abstract description 44
- 229920006026 co-polymeric resin Polymers 0.000 title abstract description 36
- -1 vinylidene halide Chemical class 0.000 title description 18
- 230000009477 glass transition Effects 0.000 claims abstract description 27
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims abstract description 20
- 239000000203 mixture Substances 0.000 claims abstract description 18
- 239000000126 substance Substances 0.000 claims abstract description 13
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims abstract description 10
- 125000005843 halogen group Chemical group 0.000 claims abstract description 5
- 238000002156 mixing Methods 0.000 claims abstract description 5
- 125000000843 phenylene group Chemical group C1(=C(C=CC=C1)*)* 0.000 claims abstract description 3
- 125000000217 alkyl group Chemical group 0.000 claims abstract 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims abstract 2
- 229920001577 copolymer Polymers 0.000 claims description 19
- 125000004432 carbon atom Chemical group C* 0.000 claims 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims 1
- 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 1
- 230000004888 barrier function Effects 0.000 abstract description 7
- 229910052736 halogen Inorganic materials 0.000 abstract description 3
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 21
- 239000000178 monomer Substances 0.000 description 19
- MYRTYDVEIRVNKP-UHFFFAOYSA-N 1,2-Divinylbenzene Chemical compound C=CC1=CC=CC=C1C=C MYRTYDVEIRVNKP-UHFFFAOYSA-N 0.000 description 18
- 238000006116 polymerization reaction Methods 0.000 description 18
- OEPOKWHJYJXUGD-UHFFFAOYSA-N 2-(3-phenylmethoxyphenyl)-1,3-thiazole-4-carbaldehyde Chemical compound O=CC1=CSC(C=2C=C(OCC=3C=CC=CC=3)C=CC=2)=N1 OEPOKWHJYJXUGD-UHFFFAOYSA-N 0.000 description 15
- HIDBROSJWZYGSZ-UHFFFAOYSA-N 1-phenylpyrrole-2,5-dione Chemical compound O=C1C=CC(=O)N1C1=CC=CC=C1 HIDBROSJWZYGSZ-UHFFFAOYSA-N 0.000 description 11
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 11
- 238000000034 method Methods 0.000 description 8
- 238000010521 absorption reaction Methods 0.000 description 7
- 230000007423 decrease Effects 0.000 description 7
- 239000006260 foam Substances 0.000 description 7
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical group C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 6
- 239000007789 gas Substances 0.000 description 6
- 239000011248 coating agent Substances 0.000 description 5
- 238000000576 coating method Methods 0.000 description 5
- 229910052757 nitrogen Inorganic materials 0.000 description 5
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 description 4
- 238000001125 extrusion Methods 0.000 description 4
- BQCIDUSAKPWEOX-UHFFFAOYSA-N 1,1-Difluoroethene Chemical compound FC(F)=C BQCIDUSAKPWEOX-UHFFFAOYSA-N 0.000 description 3
- KPQOXMCRYWDRSB-UHFFFAOYSA-N 1-(2-chlorophenyl)pyrrole-2,5-dione Chemical compound ClC1=CC=CC=C1N1C(=O)C=CC1=O KPQOXMCRYWDRSB-UHFFFAOYSA-N 0.000 description 3
- QYOJZFBQEAZNEW-UHFFFAOYSA-N 1-(2-methylphenyl)pyrrole-2,5-dione Chemical compound CC1=CC=CC=C1N1C(=O)C=CC1=O QYOJZFBQEAZNEW-UHFFFAOYSA-N 0.000 description 3
- 238000005033 Fourier transform infrared spectroscopy Methods 0.000 description 3
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 3
- 210000004027 cell Anatomy 0.000 description 3
- 239000006185 dispersion Substances 0.000 description 3
- 150000002148 esters Chemical class 0.000 description 3
- 238000012545 processing Methods 0.000 description 3
- 239000007870 radical polymerization initiator Substances 0.000 description 3
- 229920005604 random copolymer Polymers 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- BQTPKSBXMONSJI-UHFFFAOYSA-N 1-cyclohexylpyrrole-2,5-dione Chemical compound O=C1C=CC(=O)N1C1CCCCC1 BQTPKSBXMONSJI-UHFFFAOYSA-N 0.000 description 2
- LGJCFVYMIJLQJO-UHFFFAOYSA-N 1-dodecylperoxydodecane Chemical compound CCCCCCCCCCCCOOCCCCCCCCCCCC LGJCFVYMIJLQJO-UHFFFAOYSA-N 0.000 description 2
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 description 2
- SXZSFWHOSHAKMN-UHFFFAOYSA-N 2,3,4,4',5-Pentachlorobiphenyl Chemical compound C1=CC(Cl)=CC=C1C1=CC(Cl)=C(Cl)C(Cl)=C1Cl SXZSFWHOSHAKMN-UHFFFAOYSA-N 0.000 description 2
- XFCMNSHQOZQILR-UHFFFAOYSA-N 2-[2-(2-methylprop-2-enoyloxy)ethoxy]ethyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCCOCCOC(=O)C(C)=C XFCMNSHQOZQILR-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 2
- CERQOIWHTDAKMF-UHFFFAOYSA-M Methacrylate Chemical compound CC(=C)C([O-])=O CERQOIWHTDAKMF-UHFFFAOYSA-M 0.000 description 2
- 239000002202 Polyethylene glycol Substances 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 150000001735 carboxylic acids Chemical class 0.000 description 2
- 239000003610 charcoal Substances 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 125000004386 diacrylate group Chemical group 0.000 description 2
- STVZJERGLQHEKB-UHFFFAOYSA-N ethylene glycol dimethacrylate Substances CC(=C)C(=O)OCCOC(=O)C(C)=C STVZJERGLQHEKB-UHFFFAOYSA-N 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 239000003063 flame retardant Substances 0.000 description 2
- 238000005227 gel permeation chromatography Methods 0.000 description 2
- 229920001223 polyethylene glycol Polymers 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- ZTHZEDRPKCLGAR-UHFFFAOYSA-N 1-(2-bromophenyl)pyrrole-2,5-dione Chemical compound BrC1=CC=CC=C1N1C(=O)C=CC1=O ZTHZEDRPKCLGAR-UHFFFAOYSA-N 0.000 description 1
- LJDGDRYFCIHDPX-UHFFFAOYSA-N 1-(2-methoxyphenyl)pyrrole-2,5-dione Chemical compound COC1=CC=CC=C1N1C(=O)C=CC1=O LJDGDRYFCIHDPX-UHFFFAOYSA-N 0.000 description 1
- ZDQNWDNMNKSMHI-UHFFFAOYSA-N 1-[2-(2-prop-2-enoyloxypropoxy)propoxy]propan-2-yl prop-2-enoate Chemical compound C=CC(=O)OC(C)COC(C)COCC(C)OC(=O)C=C ZDQNWDNMNKSMHI-UHFFFAOYSA-N 0.000 description 1
- 150000003923 2,5-pyrrolediones Chemical class 0.000 description 1
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- HWSSEYVMGDIFMH-UHFFFAOYSA-N 2-[2-[2-(2-methylprop-2-enoyloxy)ethoxy]ethoxy]ethyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCCOCCOCCOC(=O)C(C)=C HWSSEYVMGDIFMH-UHFFFAOYSA-N 0.000 description 1
- WDQMWEYDKDCEHT-UHFFFAOYSA-N 2-ethylhexyl 2-methylprop-2-enoate Chemical compound CCCCC(CC)COC(=O)C(C)=C WDQMWEYDKDCEHT-UHFFFAOYSA-N 0.000 description 1
- OMIGHNLMNHATMP-UHFFFAOYSA-N 2-hydroxyethyl prop-2-enoate Chemical compound OCCOC(=O)C=C OMIGHNLMNHATMP-UHFFFAOYSA-N 0.000 description 1
- DBCAQXHNJOFNGC-UHFFFAOYSA-N 4-bromo-1,1,1-trifluorobutane Chemical compound FC(F)(F)CCCBr DBCAQXHNJOFNGC-UHFFFAOYSA-N 0.000 description 1
- FIHBHSQYSYVZQE-UHFFFAOYSA-N 6-prop-2-enoyloxyhexyl prop-2-enoate Chemical compound C=CC(=O)OCCCCCCOC(=O)C=C FIHBHSQYSYVZQE-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 1
- 125000006414 CCl Chemical group ClC* 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- JIGUQPWFLRLWPJ-UHFFFAOYSA-N Ethyl acrylate Chemical compound CCOC(=O)C=C JIGUQPWFLRLWPJ-UHFFFAOYSA-N 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 1
- GHAZCVNUKKZTLG-UHFFFAOYSA-N N-ethyl-succinimide Natural products CCN1C(=O)CCC1=O GHAZCVNUKKZTLG-UHFFFAOYSA-N 0.000 description 1
- HDFGOPSGAURCEO-UHFFFAOYSA-N N-ethylmaleimide Chemical compound CCN1C(=O)C=CC1=O HDFGOPSGAURCEO-UHFFFAOYSA-N 0.000 description 1
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 1
- BZHJMEDXRYGGRV-UHFFFAOYSA-N Vinyl chloride Chemical compound ClC=C BZHJMEDXRYGGRV-UHFFFAOYSA-N 0.000 description 1
- ULQMPOIOSDXIGC-UHFFFAOYSA-N [2,2-dimethyl-3-(2-methylprop-2-enoyloxy)propyl] 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCC(C)(C)COC(=O)C(C)=C ULQMPOIOSDXIGC-UHFFFAOYSA-N 0.000 description 1
- OQHMGFSAURFQAF-UHFFFAOYSA-N [2-hydroxy-3-(2-methylprop-2-enoyloxy)propyl] 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCC(O)COC(=O)C(C)=C OQHMGFSAURFQAF-UHFFFAOYSA-N 0.000 description 1
- XYLMUPLGERFSHI-UHFFFAOYSA-N alpha-Methylstyrene Chemical compound CC(=C)C1=CC=CC=C1 XYLMUPLGERFSHI-UHFFFAOYSA-N 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 238000012662 bulk polymerization Methods 0.000 description 1
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 description 1
- 238000011088 calibration curve Methods 0.000 description 1
- 238000007707 calorimetry Methods 0.000 description 1
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 1
- 210000000170 cell membrane Anatomy 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- HRYZWHHZPQKTII-UHFFFAOYSA-N chloroethane Chemical compound CCCl HRYZWHHZPQKTII-UHFFFAOYSA-N 0.000 description 1
- 230000006835 compression Effects 0.000 description 1
- 238000007906 compression Methods 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 238000000113 differential scanning calorimetry Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000007720 emulsion polymerization reaction Methods 0.000 description 1
- 125000002573 ethenylidene group Chemical group [*]=C=C([H])[H] 0.000 description 1
- SUPCQIBBMFXVTL-UHFFFAOYSA-N ethyl 2-methylprop-2-enoate Chemical compound CCOC(=O)C(C)=C SUPCQIBBMFXVTL-UHFFFAOYSA-N 0.000 description 1
- 229960003750 ethyl chloride Drugs 0.000 description 1
- 125000000816 ethylene group Chemical group [H]C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 238000005187 foaming Methods 0.000 description 1
- 238000010528 free radical solution polymerization reaction Methods 0.000 description 1
- 235000011389 fruit/vegetable juice Nutrition 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- VOZRXNHHFUQHIL-UHFFFAOYSA-N glycidyl methacrylate Chemical compound CC(=C)C(=O)OCC1CO1 VOZRXNHHFUQHIL-UHFFFAOYSA-N 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 238000004128 high performance liquid chromatography Methods 0.000 description 1
- 229920003088 hydroxypropyl methyl cellulose Polymers 0.000 description 1
- UFVKGYZPFZQRLF-UHFFFAOYSA-N hydroxypropyl methyl cellulose Chemical compound OC1C(O)C(OC)OC(CO)C1OC1C(O)C(O)C(OC2C(C(O)C(OC3C(C(O)C(O)C(CO)O3)O)C(CO)O2)O)C(CO)O1 UFVKGYZPFZQRLF-UHFFFAOYSA-N 0.000 description 1
- 235000010979 hydroxypropyl methyl cellulose Nutrition 0.000 description 1
- 239000001866 hydroxypropyl methyl cellulose Substances 0.000 description 1
- 239000003999 initiator Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- YDKNBNOOCSNPNS-UHFFFAOYSA-N methyl 1,3-benzoxazole-2-carboxylate Chemical compound C1=CC=C2OC(C(=O)OC)=NC2=C1 YDKNBNOOCSNPNS-UHFFFAOYSA-N 0.000 description 1
- SEEYREPSKCQBBF-UHFFFAOYSA-N n-methylmaleimide Chemical compound CN1C(=O)C=CC1=O SEEYREPSKCQBBF-UHFFFAOYSA-N 0.000 description 1
- 238000009840 oxygen flask method Methods 0.000 description 1
- 229920006280 packaging film Polymers 0.000 description 1
- 239000012785 packaging film Substances 0.000 description 1
- PNJWIWWMYCMZRO-UHFFFAOYSA-N pent‐4‐en‐2‐one Natural products CC(=O)CC=C PNJWIWWMYCMZRO-UHFFFAOYSA-N 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 230000000379 polymerizing effect Effects 0.000 description 1
- 229920005651 polypropylene glycol dimethacrylate Polymers 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- BWJUFXUULUEGMA-UHFFFAOYSA-N propan-2-yl propan-2-yloxycarbonyloxy carbonate Chemical compound CC(C)OC(=O)OOC(=O)OC(C)C BWJUFXUULUEGMA-UHFFFAOYSA-N 0.000 description 1
- 238000010926 purge Methods 0.000 description 1
- 238000000197 pyrolysis Methods 0.000 description 1
- 238000000045 pyrolysis gas chromatography Methods 0.000 description 1
- 238000011002 quantification Methods 0.000 description 1
- 238000004445 quantitative analysis Methods 0.000 description 1
- 238000010526 radical polymerization reaction Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 239000000375 suspending agent Substances 0.000 description 1
- 238000010557 suspension polymerization reaction Methods 0.000 description 1
- 230000008961 swelling Effects 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 238000005979 thermal decomposition reaction Methods 0.000 description 1
- 239000002937 thermal insulation foam Substances 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Landscapes
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
Description
【発明の詳細な説明】
〔産業上の利用分野〕
本発明は、耐熱変形性、難燃性、ガスバリア性、耐薬品
性、熱可塑性を有するハロゲン化ビニリデン系共重合体
樹脂組成物に関する０本発明のハロゲン化ビニリデン系
共重合体樹脂組成物は、フィルム、シート、フオーム又
は成形品に利用することができる。Detailed Description of the Invention [Field of Industrial Application] The present invention relates to a vinylidene halide copolymer resin composition having heat deformation resistance, flame retardance, gas barrier properties, chemical resistance, and thermoplasticity. The vinylidene halide copolymer resin composition of the invention can be used for films, sheets, foams, or molded articles.
ハロゲン化ビニリデン系共重合体は、結晶性を有する結
晶性共重合体と結晶性を有しない非品性共重合体とに分
類される。Vinylidene halide copolymers are classified into crystalline copolymers that have crystallinity and non-quality copolymers that do not have crystallinity.
結晶性共重合体は、ハロゲン化ビニリデン構造単位の含
有率が８５モル％より多い領域のものであり、熔融押出
成膜、溶剤溶液塗布、水性分散液塗布、他の樹脂と混合
して成形加工する等の方法により難燃性、ガスバリア性
、耐薬品性等の特性を生かした繊維、食品包装フィルム
、シート、断熱材フオーム、チューブやカップ等の成形
品等に加工され利用されている。難燃性、ガスバリア性
、耐薬品性等の特性を極力維持させて主として結晶性で
あるが故に起こる熔融押出成膜時のフィルム寸法安定性
制御の困難さ、溶融押出時の難溶融性、溶剤溶液塗布で
の溶剤への難溶解性や塗液の短寿命、水性分散液塗布で
の分散液の短寿命等の問題を解決しようとする試みや提
案がなされている。The crystalline copolymer has a vinylidene halide structural unit content of more than 85 mol%, and can be formed by melt extrusion, solvent solution coating, aqueous dispersion coating, or mixing with other resins to form the copolymer. It is processed into fibers, food packaging films, sheets, insulation foams, and molded products such as tubes and cups that take advantage of their properties such as flame retardancy, gas barrier properties, and chemical resistance. While maintaining properties such as flame retardancy, gas barrier properties, and chemical resistance as much as possible, it is difficult to control the dimensional stability of the film during melt extrusion film formation due to its crystallinity, difficulty in melting during melt extrusion, and solvents. Attempts and proposals have been made to solve problems such as poor solubility in solvents and short life of the coating liquid in solution coating, and short life of the dispersion in aqueous dispersion coating.
特開昭６０−４４５１０号公報には、共重合体が結晶性
であるために起こる問題点を解決するために非品性領域
のハロゲン化ビニリデン共重合体が提案されている。そ
こには、塩化ビニリデン／メチルアクリレートがモル％
比で４７１５３〜８１／１９の仕込組成で重合して得ら
れた共重合体が可塑剤を添加することなく熔融押出成膜
できた例などが挙げられている。しかし、共重合体のガ
ラス転移点が低いために、これより得られたフィルムや
フオームは高温での腰が弱く、耐熱変形性に乏しい。Japanese Unexamined Patent Publication No. 60-44510 proposes a vinylidene halide copolymer of low quality in order to solve problems caused by the crystallinity of the copolymer. It contains vinylidene chloride/methyl acrylate in mole%
An example is given in which a copolymer obtained by polymerization with a feed composition having a ratio of 47153 to 81/19 could be melt-extruded into a film without adding a plasticizer. However, since the copolymer has a low glass transition point, the films and foams obtained from it are weak at high temperatures and have poor heat deformation resistance.
本発明の目的は、耐熱変形性、難燃性に優れ、ガスバリ
ア性、耐薬品性等ハロゲン化ビニリデン系共重合体の特
性を有し、かつ、結晶性ハロゲン化ビニリデン系共重合
体の持つ前記欠点がなく、しかも８５℃以上のガラス転
移点を有する新規なハロゲン化ビニリデン系共重合体樹
脂組成物を提供することである。The object of the present invention is to have the properties of a vinylidene halide copolymer, such as excellent heat deformation resistance and flame retardancy, gas barrier properties, and chemical resistance, and the above properties of a crystalline vinylidene halide copolymer. The object of the present invention is to provide a novel vinylidene halide copolymer resin composition which is free from drawbacks and has a glass transition point of 85° C. or higher.
本発明者らは、上記目的達成のため鋭意研究の結果、本
発明に到達した。The present inventors have arrived at the present invention as a result of intensive research to achieve the above object.
即ち、本発明は、下記の一般式Ｔａｌ、（ｂ）、（Ｃ）
で表される構造単位からなり、その組成が（ａ）３０〜
７０モル％、（ｂ）１〜ｌＯモル％、（ｃ）２５〜７０
モル％である共重合体で、その重量平均分子量が１０，
０００〜６００，０００で、ガラス転移点が８０℃以上
のテトラヒドロフランに可溶な成分（Ａ）と、下記一般
式（ａ）、（ト））、（Ｃ）、（ｄ＋で表される構造単
位からなり、その組成が（ａ１２５〜６５モル％、（′
ｂ）１〜１０モル％、（ｃ）２５〜７０モル％、ｆｄｌ
０ 、０１〜０．２モル％である共重合体で、テトラ
ヒドロフランに不溶な成分（Ｂ）とからなり、成分（Ａ
）と（Ｂ）の配合割合が、
（Ａ） ＝１００− （Ｂ）
１０］ｉ量％≦（Ｂ）≦８０ｉｉ量％
であり、ガラス転移点が８５℃以上であることを特徴と
するハロゲン化ビニリデン系ランダム共重合体樹脂組成
物。That is, the present invention provides the following general formula Tal, (b), (C)
It consists of a structural unit represented by (a)30~
70 mol%, (b) 1-1O mol%, (c) 25-70
A copolymer whose weight average molecular weight is 10,
000 to 600,000 and a tetrahydrofuran-soluble component (A) with a glass transition point of 80°C or higher, and structural units represented by the following general formulas (a), (g)), (C), and (d+). The composition is (a125-65 mol%, ('
b) 1-10 mol%, (c) 25-70 mol%, fdl
0,01-0.2 mol% copolymer consisting of a component (B) insoluble in tetrahydrofuran and a component (A
) and (B) in a blending ratio of (A) = 100 - (B) 10]i amount%≦(B)≦80ii amount%, and a halogen characterized by having a glass transition point of 85°C or higher Vinylidene oxide random copolymer resin composition.
記 ＋ＣＲ２−ＣＸ、＋−（ａ） Ｒ。Record +CR2-CX, +-(a) R.
÷ＣＨニーＣ＋−（Ｃ）
Ｒ斗
〔但し、Ｘはハロゲン基、Ｒ２は炭素数１〜４のア−Ｃ
Ｉ 、Ｂ ｒ １− ＯＣＨｓ、−Ｈを表し、Ｒ２、拘
。÷CHnee C+-(C) R[However, X is a halogen group, and R2 is an a-C
I, B r 1- OCHs, -H; R2, restraint;
を表し、ｎ＝０〜８の整数で、Ｒ５はフェニレン基、Ｏ
（４）Ｔ２．Ｌｏ−（ｋは３〜６の整数）〕に関するも
のである。represents an integer of n=0 to 8, R5 is a phenylene group, O
(4) T2. Lo-(k is an integer from 3 to 6)].
本発明のランダム共重合体の構造単位（ａ）は、フン化
ビニリデン、塩化ビニリデン、臭化ビニリデンの二重結
合が開いた構造を有する単位であり、これらの単量体か
ら得られる。その中で、フン化ビニリデンと塩化ビニリ
デンが好ましく、取扱の容易な点から塩化ビニリデンが
特に好ましい。The structural unit (a) of the random copolymer of the present invention is a unit having a structure with an open double bond of vinylidene fluoride, vinylidene chloride, or vinylidene bromide, and is obtained from these monomers. Among them, vinylidene fluoride and vinylidene chloride are preferred, and vinylidene chloride is particularly preferred from the viewpoint of easy handling.
構造単位（ｂ）はＮ−置換マレイミドのンＣＨ” ＣＨ
りの二重結合が開いた構造を有する単位であり、Ｎ−置
換マレイミド単量体から得られる。Ｎ−置換マレイミド
単量体としては、Ｎ−フェニルマレイミド、Ｎ−２−メ
チルフェニルマレイミド、Ｎ−２，６−シメチルフエニ
ルマレイミド、Ｎ−シクロヘキシルマレイミド、Ｎ−２
−クロロフェニルマレイミド、Ｎ−２−ブロモフェニル
マレイミド、Ｎ−２−メトキシフェニルマレイミド、Ｎ
−エチルマレイミド等を挙げることができる。Ｎ−フェ
ニルマレイミド、Ｎ−２−メチルフェニルマレイミド、
Ｎ−２−クロロフェニルマレイミドが工業的に入手し易
く好ましい、Ｎ−フェニルマレイミドが特に好ましい。Structural unit (b) is N-substituted maleimide CH"CH
It is a unit with a structure in which the double bond is open, and is obtained from an N-substituted maleimide monomer. As the N-substituted maleimide monomer, N-phenylmaleimide, N-2-methylphenylmaleimide, N-2,6-dimethylphenylmaleimide, N-cyclohexylmaleimide, N-2
-chlorophenylmaleimide, N-2-bromophenylmaleimide, N-2-methoxyphenylmaleimide, N
-ethylmaleimide and the like. N-phenylmaleimide, N-2-methylphenylmaleimide,
N-2-chlorophenylmaleimide is preferred because it is industrially easily available, and N-phenylmaleimide is particularly preferred.
構造単位（Ｃ）は、α−モノ置換不飽和エチレン系単量
体、不飽和カルボン酸及びそのエステル系単量体のスー
Ｃくの二重結合が開いた構造を有する単位である。α−
モノ置換不飽和エチレン系単量体としては、塩化ビニル
、酢酸ビニル、スチレン、α−メチルスチレン、アクリ
ロニトリル、メタクリレートリル等を挙げることができ
、不飽和カルボン酸及びそのエステル系単量体としては
、アクリル酸、メタクリル酸、メチルアクリレート、エ
チルアクリレート、ブチルアクリレート、メチルメタク
リレート、エチルメタクリレート、グリシジルメタクリ
レート、２−エチルへキシルアタリレート、２−エチル
へキシルメタクリレート、ヒドロキシエチルアクリレー
ト等を挙げることができる。The structural unit (C) is a unit having a structure in which a double bond of an α-monosubstituted unsaturated ethylenic monomer, an unsaturated carboxylic acid, and an ester monomer thereof is open. α−
Examples of monosubstituted unsaturated ethylenic monomers include vinyl chloride, vinyl acetate, styrene, α-methylstyrene, acrylonitrile, methacrylate trile, etc., and unsaturated carboxylic acids and their ester monomers include: Examples include acrylic acid, methacrylic acid, methyl acrylate, ethyl acrylate, butyl acrylate, methyl methacrylate, ethyl methacrylate, glycidyl methacrylate, 2-ethylhexyl arylate, 2-ethylhexyl methacrylate, hydroxyethyl acrylate, and the like.
構造単位（ｄｌは、ジビニル系単量体、ジエステルアク
リレート系単量体又はジエステルメタクリレート系単量
体が持）二つのンＣ−ＣＣの二重結合が開いた構造を有
する単位である。ジビニル系単量体としては、ジビニル
ベンゼン等を挙げることができ、ジエステルアクリレー
ト系単量体としては、ポリエチレングリコールジアクリ
レート、１゜６−ヘキサンジオールジアクリレート、ネ
オペンチルグリコールジアクリレート、トリプロピレン
グリコールジアクリレート、２，２−ビス４−アクリロ
キシジエトキシフェニルブロバン等を挙げることができ
、ジエステル系メタクリレート系単量体としては、エチ
レングリコールジメタクリレート、ジエチレングリコー
ルジメタクリレート、トリエチレングリコールジメタク
リレート、ポリエチレングリコールジメタクリレート、
１．３−ブチレングリコールジメタクリレート、１，６
−ヘキサンジオールジアクリレート、ネオペンチルグリ
コールジメタクリレート、ポリプロピレングリコールジ
メタクリレート、２−ヒドロキシ−１，３−ジメタクリ
ロキシプロパン等を挙げることができる。The structural unit (dl is a unit possessed by a divinyl monomer, a diester acrylate monomer, or a diester methacrylate monomer) has a structure in which two C-CC double bonds are open. Examples of divinyl monomers include divinylbenzene, and examples of diester acrylate monomers include polyethylene glycol diacrylate, 1°6-hexane diol diacrylate, neopentyl glycol diacrylate, and tripropylene glycol diacrylate. acrylate, 2,2-bis4-acryloxydiethoxyphenylbroban, etc. Examples of diester methacrylate monomers include ethylene glycol dimethacrylate, diethylene glycol dimethacrylate, triethylene glycol dimethacrylate, and polyethylene glycol dimethacrylate. methacrylate,
1.3-butylene glycol dimethacrylate, 1,6
-hexanediol diacrylate, neopentyl glycol dimethacrylate, polypropylene glycol dimethacrylate, 2-hydroxy-1,3-dimethacryloxypropane, and the like.
（Ａ）における構造単位（ａｌ、（ｂｌ、（Ｃ）の結合
順序及び（Ｂ）における構造単位（ａｌ、（ｂ）、（Ｃ
）、Ｔｄ）（７）結合順序は、ラジカル重合機構で律せ
られるランダムな結合である。又、結合単位ｆｄｌは、
主として三次元構造の架橋点を形成している。Bonding order of structural units (al, (bl, (C)) in (A) and structural units (al, (b), (C) in (B)
), Td) (7) The bonding order is random bonding determined by the radical polymerization mechanism. Also, the bonding unit fdl is
It mainly forms crosslinking points in the three-dimensional structure.
ガラス転移点は、ＡＳＴＭ Ｄ−３４１８−７５に準じ
て示差熱量針（ＤＳＣ）により測定され、加工品の耐熱
変形性の目安として重要である。The glass transition point is measured using a differential calorimetry needle (DSC) according to ASTM D-3418-75, and is important as a measure of heat deformation resistance of processed products.
本発明に云うテトラヒドロフランに可溶な成分（以後単
に可溶分と云う）とテトラヒドロフランに不溶な成分（
以後単に不溶分と云う）とは、本発明の共重合体樹脂組
成物１〜２ｇを１００ｍ１のテトラヒドロフラン中に４
０℃、１時間攪拌下に浸漬させた後、可溶分と不溶分を
濾別し、テトラヒドロフランを除去することによりそれ
ぞれ得られる共重合体のことである。In the present invention, components soluble in tetrahydrofuran (hereinafter simply referred to as soluble components) and components insoluble in tetrahydrofuran (
Hereinafter simply referred to as insoluble matter), 1 to 2 g of the copolymer resin composition of the present invention is dissolved in 100 ml of tetrahydrofuran.
These copolymers are obtained by immersing the polymer under stirring at 0° C. for 1 hour, filtering off the soluble and insoluble components, and removing tetrahydrofuran.
本発明の共重合体樹脂組成物中の可溶分の含有量が増す
と、共重合体樹脂組成物の溶融流動性が高まる。一方、
不溶分の含有量が増すと、共重合樹脂組成物の高温での
引張強度は向上するが、伸度は低下する傾向になる。When the content of soluble components in the copolymer resin composition of the present invention increases, the melt flowability of the copolymer resin composition increases. on the other hand,
As the content of insoluble matter increases, the tensile strength at high temperatures of the copolymer resin composition increases, but the elongation tends to decrease.
可溶分及び不溶分の好ましい含有量は、目的とする加工
品により選ばれるべきものであり、例えば、本発明の共
重合体樹脂組成物をフィルムに加工する場合には、流動
性に重点を置く必要があるので、不溶分の比較的少ない
共重合体樹脂組成物が適しており、不溶分含有量は１０
〜４０ｆｉ量％が好ましく、又、フオームに加工する場
合には、発泡過程で独立気泡を維持させるためにセル膜
の強度を高くする必要があるので、不溶分の比較的多い
共重合体樹脂組成物が適しており、不溶分含有量は３０
〜８０ｆｆｉ量％好ましくは３０〜６０重量％である。The preferred contents of soluble and insoluble components should be selected depending on the intended processed product. For example, when processing the copolymer resin composition of the present invention into a film, emphasis should be placed on fluidity. Therefore, a copolymer resin composition with a relatively low insoluble content is suitable, and the insoluble content is 10
~40 fi amount% is preferable, and when processing into foam, it is necessary to increase the strength of the cell membrane in order to maintain closed cells during the foaming process, so the copolymer resin composition has a relatively large amount of insoluble content. is suitable, and the insoluble content is 30
~80ffi amount%, preferably 30-60% by weight.
可溶分の重量平均分子量は、１０．０００〜６００，０
００である。分子量はゲルパーミェーションクロマトグ
ラフィー（ＧＰＣ、東洋曹達工業ＨＰＬＣ８０２型）に
より測定される。重量平均分子量が１０，０００未満で
は共重合体は油状、ペースト状、或いは強伸度等の機械
的物性が低い共重合体となり、成形品等に使用できず実
用的でない。重量平均分子量が６００゜ＯＯＯを越える
と、熔融押出成膜等の加工が困難となり好ましくない。The weight average molecular weight of the soluble portion is 10.000 to 600.0
It is 00. The molecular weight is measured by gel permeation chromatography (GPC, Toyo Soda Kogyo HPLC model 802). When the weight average molecular weight is less than 10,000, the copolymer becomes oily, paste-like, or has low mechanical properties such as strength and elongation, and cannot be used for molded products and is therefore impractical. If the weight average molecular weight exceeds 600°OOO, processing such as melt extrusion film formation becomes difficult, which is not preferable.
又ガラス転移点は８０℃以上である。８０℃未満では共
重合体組成物の耐熱変形性が劣る。Further, the glass transition point is 80°C or higher. If the temperature is lower than 80°C, the heat deformation resistance of the copolymer composition is poor.
本発明の共重合体樹脂組成物の可溶分における各単位の
組成は次の範囲である。The composition of each unit in the soluble component of the copolymer resin composition of the present invention is within the following range.
（ａ１３０〜７０モル％、（ｂ）１〜１０モル％、（Ｃ
）２５〜７０モル％
（ａ）が３０モル％未満では共重合体樹脂組成物の難燃
性、ガスバリア性の特性を生かすことができなくなり、
７０モル％を越えると耐熱変形性が低下する。好ましい
範囲は３５〜６０モル％である。 （ｂ）が１モル％未
満では耐熱変形性が低下し好ましくない。(a130-70 mol%, (b) 1-10 mol%, (C
) 25 to 70 mol% If (a) is less than 30 mol%, the flame retardant and gas barrier properties of the copolymer resin composition cannot be utilized;
If it exceeds 70 mol%, heat deformation resistance will decrease. The preferred range is 35 to 60 mol%. If (b) is less than 1 mol %, heat deformation resistance decreases, which is not preferable.
一方、１０モル％を越えたランダム共重合体を得ること
は困難であり、又仮に得ることができたとしても高価で
あり経済的でない。好ましい範囲は１〜８モル％である
。（Ｃ）が２５モル％未満では耐熱変形性が低下し、７
０モル％を越えると共重合体樹脂組成物の特性が低下し
好ましくない。好ましい範囲は３５〜６５モル％である
。On the other hand, it is difficult to obtain a random copolymer with a content exceeding 10 mol %, and even if it could be obtained, it is expensive and uneconomical. The preferred range is 1 to 8 mol%. When (C) is less than 25 mol%, heat deformation resistance decreases, and 7
If it exceeds 0 mol%, the properties of the copolymer resin composition will deteriorate, which is not preferable. The preferred range is 35 to 65 mol%.
不溶分における各構造単位の組成は次の範囲である。The composition of each structural unit in the insoluble matter is within the following range.
＋ａ１２５〜６５モル％、（ｂ）１〜１０モル％、（Ｃ
）２５〜７０モル％、（ｄｌＯ，０１〜０．２モル％。+a125-65 mol%, (b) 1-10 mol%, (C
)25-70 mol%, (dlO, 01-0.2 mol%.
（ａ）が３０モル％未満では難燃性、ガスバリア性の特
性を生かすことができなくなり、６５モル％を越えると
耐熱変形性が低下する。好ましい範囲は３０〜６０モル
％である。（ｂｌが１モル％未満では耐熱変形性が低下
し、１０モル％を越えるとハロゲン化ビニリデン共重合
体樹脂組成物の固有の特性を低下させる。好ましい範囲
は１〜８モル％である。ｔｃ＋が２５モル％未満では耐
熱変形性が低下し、７０モル％を越えるとハロゲン化ビ
ニリデン共重合体樹脂組成物の固有の特性が低下し好ま
しくない。好ましい範囲は３５〜６５モル％である。（
ｄ）が０．０１モル％未満であるとハロゲン化ビニリデ
ン共重合体樹脂組成物において不溶分が示す効果が期待
できなくなり、０．２モル％を越えると高温での伸度が
著しく低下する。好ましい範囲は０６０１〜０．１モル
％である。If (a) is less than 30 mol %, the flame retardant and gas barrier properties cannot be utilized, and if it exceeds 65 mol %, the heat deformation resistance decreases. The preferred range is 30 to 60 mol%. (If bl is less than 1 mol%, the heat deformation resistance will decrease, and if it exceeds 10 mol%, the inherent properties of the vinylidene halide copolymer resin composition will be degraded. The preferable range is 1 to 8 mol%. tc+ If it is less than 25 mol%, the heat deformation resistance will decrease, and if it exceeds 70 mol%, the inherent properties of the vinylidene halide copolymer resin composition will deteriorate, which is undesirable.The preferred range is 35 to 65 mol%.
If d) is less than 0.01 mol %, the effect of the insoluble matter in the vinylidene halide copolymer resin composition cannot be expected, and if it exceeds 0.2 mol %, the elongation at high temperatures will be significantly reduced. The preferred range is 0.601 to 0.1 mol%.
本発明の共重合体樹脂組成物は、フン化ビニリデン、塩
化ビニリデン、臭化ビニリデンの１種以上及び前記Ｎ−
置換マレイミドの１種以上及び前記α−モノ置換エチレ
ン系単量体、不飽和カルボン酸及びそのエステル系単量
体の１種以上及び前記ジビニル系単量体、ジアクリレー
ト系単量体、ジメタクリレート系単量体の１種以上をラ
ジカル重合することにより製造することができる。The copolymer resin composition of the present invention comprises one or more of vinylidene fluoride, vinylidene chloride, vinylidene bromide and the above-mentioned N-
One or more substituted maleimides, one or more of the α-monosubstituted ethylene monomers, unsaturated carboxylic acids and their ester monomers, and the divinyl monomers, diacrylate monomers, dimethacrylates It can be produced by radical polymerizing one or more type monomers.
重合方法は公知の懸濁重合、乳化重合、溶液重合、塊状
重合等の諸方法を採用することができる。As the polymerization method, various known methods such as suspension polymerization, emulsion polymerization, solution polymerization, and bulk polymerization can be employed.
ラジカル重合開始剤としては、加熱により分解してラジ
カルを発生するすべての開始剤を使用することができる
。例えば、比較的低温で重合させるためには、ジイソプ
ロピルパーオキシジカーボネートが、比較的高温で重合
させるためには、ラウリルパーオキサイドが周知である
。As the radical polymerization initiator, any initiator that can be decomposed by heating to generate radicals can be used. For example, diisopropyl peroxydicarbonate is well known for polymerization at relatively low temperatures, and lauryl peroxide is known for polymerization at relatively high temperatures.
重合温度、重合時間は、使用するラジカル重合開始剤及
び重合熱除去、収率等を勘案して適宜選択することがで
きる。The polymerization temperature and polymerization time can be appropriately selected in consideration of the radical polymerization initiator used, polymerization heat removal, yield, etc.
又、本発明の共重合体樹脂組成物は、（Ａ）、ＣＢ）そ
れぞれを上記の重合方法により予め作成して置き、ブレ
ンドさせることによっても製造することができる。The copolymer resin composition of the present invention can also be produced by preparing each of (A) and CB) in advance by the above polymerization method and blending them.
次に本発明の耐熱変形性ハロゲン化ビニリデン系共重合
体について実施例を挙げて更に詳しく説明するが、本発
明の範囲はその内容のみに固定されない。実施例におけ
る部は重量部である。Next, the heat deformation-resistant vinylidene halide copolymer of the present invention will be described in more detail with reference to Examples, but the scope of the present invention is not limited to the content thereof. Parts in the examples are parts by weight.
実施例１
反応容器に純水１５０部、懸濁剤としてヒドロキシプロ
ピルメチルセルロース０．２部ヲ仕込む。次にＮ−フェ
ニルマレイミド５部（２，４モル％）をアクリロニトリ
ル３０部（４５，１モル％）とスチレン１５部（１），
４モル％）、ジビニルベンゼン０．０４部（０゜０２５
モル％）に予め熔解させ、更に塩化ビニリデン５０部（
４１，１モル％）を溶解させた単量体混合物とラジカル
重合開始剤としてラウリルパーオキサイド０．６部を添
加する。窒素置換後、攪拌を開始し、６０℃で２４時間
反応させる。重合終了後、生成ポリマーを濾過分離し、
乾燥させる。残存単量体０．２％以下に処理した。Example 1 A reaction vessel was charged with 150 parts of pure water and 0.2 parts of hydroxypropylmethylcellulose as a suspending agent. Next, 5 parts (2.4 mol%) of N-phenylmaleimide, 30 parts (45.1 mol%) of acrylonitrile and 15 parts (1) of styrene,
4 mol%), divinylbenzene 0.04 part (0°025
mol%), and then 50 parts of vinylidene chloride (mol%).
41.1 mol %) and 0.6 part of lauryl peroxide as a radical polymerization initiator are added. After purging with nitrogen, stirring is started and the reaction is carried out at 60° C. for 24 hours. After the polymerization is completed, the produced polymer is separated by filtration,
dry. The residual monomer content was reduced to 0.2% or less.
重合率は９８％であった。ガラス転移点はＤＳＣ分析に
よると９６℃であった。可溶分の含有量は４１Ｍ量％、
不溶分の含有量は５９重量％である。可溶分のガラス転
移点は８３℃であった。The polymerization rate was 98%. The glass transition point was 96° C. according to DSC analysis. The content of soluble matter is 41M%,
The content of insoluble matter is 59% by weight. The glass transition point of the soluble component was 83°C.
得られた共重合体樹脂組成物、可溶分及び不溶分の定性
、定量法は以下の方法を使用した。The following methods were used to qualitatively and quantitatively determine the soluble and insoluble components of the resulting copolymer resin composition.
塩化ビニリデンからの構造単位は、熱分解ガスクロマト
グラフィー（ＰＧＣＳ熱分解炉装置（日本分光工業ＪＨ
Ｐ−２型）、ガスクロ（島津ＧＣ−４ＢＦｌ型）〕法に
より定性を行い、塩素分析法（酸素フラスコ燃焼法）に
より定量を行った。Structural units from vinylidene chloride can be extracted using pyrolysis gas chromatography (PGCS pyrolysis furnace equipment (JH
P-2 type), gas chromatography (Shimadzu GC-4BFl type)] method, and quantitative determination was performed using a chlorine analysis method (oxygen flask combustion method).
Ｎ−フェニルマレイミドからの構造単位に関しては、フ
ーリエ変換赤外吸収スペクトル（ＦＴ−ＩＲ１日本分光
工業ＦＴ−ＩＲａ型）法により定性、定量を行った。Ｃ
−Ｎの伸縮振動に基づく吸収帯が１３８８ｃｍ”及びＣ
＝Ｏの伸縮振動に基づく吸収帯が１７１２ｃｍ−’に観
察され、Ｃ＝Ｏの吸収ピークを塩化ビニリデンからの構
造単位のＣ−Ｃｌ伸縮振動に基づ＜１０６４ｃｍ”の吸
収ピークの比より定量した。The structural unit derived from N-phenylmaleimide was qualitatively and quantitatively determined by Fourier transform infrared absorption spectroscopy (FT-IR1 JASCO Corporation FT-IRa model). C
-The absorption band based on the stretching vibration of N is 1388 cm” and C
An absorption band based on the stretching vibration of =O was observed at 1712 cm-', and the absorption peak of C=O was quantified from the ratio of the absorption peak at <1064 cm'' based on the C-Cl stretching vibration of the structural unit from vinylidene chloride. .
アクリロニトリルからの構造単位は、ＰＧＣ法により定
性を行い、ＦＴ−ＩＨにより定量を行った。アクリロニ
トリルの構造単位からくるＣ＝Ｎの伸縮振動である２２
２５ｃｍ＝吸収ピーク色吸収６４ｃｍ−’の吸収ピーク
より定量した。The structural unit derived from acrylonitrile was qualitatively determined by PGC method and quantitatively determined by FT-IH. 22 which is the stretching vibration of C=N coming from the structural unit of acrylonitrile.
Quantification was determined from the absorption peak at 25 cm=absorption peak color absorption 64 cm-'.
スチレンからの構造単位は、ＰＧＣ法により定性、定量
を行った。熱分解により得られたスチレン単量体の特性
ピークの高さより定量した。The structural unit from styrene was qualitatively and quantitatively determined by the PGC method. It was determined based on the height of the characteristic peak of styrene monomer obtained by thermal decomposition.
ジビニルベンゼンからの構造単位の定性、定量は、テト
ラヒドロフランの共重合体樹脂組成物への膨潤炭より行
った。含有量と膨潤炭の関係は予め検量線より求められ
る。Qualitative and quantitative determination of structural units from divinylbenzene was carried out using swollen charcoal added to a copolymer resin composition of tetrahydrofuran. The relationship between the content and the swelling charcoal can be determined in advance from a calibration curve.
第１図、第２図に共重合体樹脂組成物のＰＧＣチャート
、ＦＴ−ＩＲチャートを示した。FIG. 1 and FIG. 2 show the PGC chart and FT-IR chart of the copolymer resin composition.
上記の定性、定量法により得られた共重合体樹脂組成物
の可溶分（Ａ）、不溶分ＣＢ）の構造単位の組成は以下
の値であった。The compositions of the structural units of the soluble component (A) and insoluble component CB) of the copolymer resin composition obtained by the above qualitative and quantitative methods were as follows.
（Ａ）： ＋ＣＨ，−ＣＣＩ、÷ ４４モル％、
（Ｂ）： ＋ＣＨ，−ＣＣＩユ± ３９モル％、
この共重合体樹脂組成物にフロン１）の９０重量％とエ
チルクロライド１０重量％の混合物を１００℃で４４時
間含浸させる。その含浸されたものを０．８ Ｋｇ／Ｃ
１）！ （ゲージ圧）の蒸気により発泡させたところ、
独立気泡率１００％の発泡体ができた。(A): +CH, -CCI, ÷ 44 mol%,
(B): +CH, -CCI unit ± 39 mol%,
This copolymer resin composition is impregnated with a mixture of 90% by weight of Freon 1) and 10% by weight of ethyl chloride at 100° C. for 44 hours. The impregnated material is 0.8 Kg/C
1)! (gauge pressure) steam was used to foam the foam.
A foam with a closed cell ratio of 100% was produced.
実施例２
塩化ビニリデン５０部（４１，１モル％）、Ｎ−フェニ
ルマレイミド５部（２，４モル％）、アクリロニトリル
３０部（４５，１モル％）、スチレン１５部（１），４
モル％）、ジビニルベンゼン０．０２Ｂ （０，０１３
モル％）を実施例１と同様に反応、処理した。Example 2 50 parts of vinylidene chloride (41.1 mol%), 5 parts of N-phenylmaleimide (2.4 mol%), 30 parts of acrylonitrile (45.1 mol%), 15 parts of styrene (1), 4
mol%), divinylbenzene 0.02B (0,013
% by mole) was reacted and treated in the same manner as in Example 1.
重合率は９８％であった。得られた樹脂組成物のガラス
転移点は９６℃、可溶分のガラス転移点は８９℃、重量
平均分子量は３９０．０００であった。可溶分（Ａ）と
不溶分（Ｂ）の共重合体樹脂組成物の組成は以下の値で
あった。The polymerization rate was 98%. The resulting resin composition had a glass transition point of 96°C, a soluble component had a glass transition point of 89°C, and a weight average molecular weight of 390.000. The composition of the copolymer resin composition of soluble portion (A) and insoluble portion (B) was as follows.
（Ａ）： ＋ＣＨｉ−ＣＣ１２± ４３モル％、
（Ｂ）： −（−ＣＨ２−ＣＣＩ、士 ３６モル
％、結果を第１表に示す。(A): +CHi-CC12±43 mol%,
(B): -(-CH2-CCI, 36 mol%, results are shown in Table 1.
得られた共重合体樹脂組成物を圧縮成形し、０．２〜０
．４ｍｍ厚みのシートから巾５ｍｍ５長さ５０ｍｍ （
チャック間距離）の試験片を切出し、１２０℃において
引張速度２００ｍｍ ／ｍｉｎで引張った。破断強度は
０．２８Ｋｇ／ｍ＃であった。The obtained copolymer resin composition was compression molded and
．． Width 5mm 5 length 50mm from a 4mm thick sheet (
A test piece was cut out (distance between chucks) and pulled at 120° C. at a pulling speed of 200 mm /min. The breaking strength was 0.28 Kg/m#.
実施例３
塩化ビニリデン５０部（４１，１モル％）、Ｎ−２−メ
チルフェニルマレイミド５部（２，２モル％）、アクリ
ロニトリル３０部（４５，２モル％）、スチレン１５部
（１），５モル％）、ジビニルベンゼン０．０２部（０
，０１３モル％）を実施例１と同様に反応、処理した。Example 3 50 parts of vinylidene chloride (41.1 mol%), 5 parts of N-2-methylphenylmaleimide (2.2 mol%), 30 parts of acrylonitrile (45.2 mol%), 15 parts of styrene (1), 5 mol%), divinylbenzene 0.02 part (0
, 013 mol %) was reacted and treated in the same manner as in Example 1.
重合率は９８％であった。得られた樹脂組成物のガラス
転移点は９８℃、可溶分のガラス転移点は９１℃、重量
平均分子量は３７６、０００であった。可溶分（Ａ）と
不溶分（Ｂ）の共重合体樹脂組成物の組成は以下の値で
あった。The polymerization rate was 98%. The resulting resin composition had a glass transition point of 98°C, a soluble component had a glass transition point of 91°C, and a weight average molecular weight of 376,000. The composition of the copolymer resin composition of soluble portion (A) and insoluble portion (B) was as follows.
（Ａ）： ＋ＣＨ，−ＣＣＩ、−← ４３モル％
、（Ｂ）：＋ＣＨニーＣＣｌ２す ３６モル％、＋
ｃ Ｈ，−ＣＨ← ３９モル％Ｎ
結果を第１表に示す。(A): +CH, -CCI, -← 43 mol%
, (B): +CH-CCl2 36 mol%, +
c H, -CH← 39 mol% N The results are shown in Table 1.
実施例４
塩化ビニリデン５０部（４１，７モル％）、Ｎ−フェニ
ルマレイミド１０部（４，７モル％）、アクリロニトリ
ル３０部（４５，８モル％）、スチレン１０部（７，８
モル％）、ジビニルベンゼン０．０４部（０，０２５モ
ル％）を実施例１と同様に反応、処理した。Example 4 50 parts of vinylidene chloride (41.7 mol%), 10 parts of N-phenylmaleimide (4.7 mol%), 30 parts of acrylonitrile (45.8 mol%), 10 parts of styrene (7.8 mol%)
%) and 0.04 part (0,025 mol%) of divinylbenzene were reacted and treated in the same manner as in Example 1.
重合率は９６％であった。得られた樹脂組成物のガラス
転移点は１０２℃、可溶分のガラス転移点は８８℃、重
量平均分子量は２２２．０００であった。可溶分（Ａ）
と不溶分（Ｂ）の共重合体樹脂組成物の組成は以下の値
であった。The polymerization rate was 96%. The resulting resin composition had a glass transition point of 102°C, a soluble component had a glass transition point of 88°C, and a weight average molecular weight of 222.000. Soluble content (A)
The composition of the copolymer resin composition of and insoluble portion (B) was as follows.
（Ａ）： ＋ＣＨＬ−ＣＣＩ２＋ ４５モル％
、−ｅ−ＣＨ，−ＣＨ＋４５モル％
Ｎ
（Ｂ）： −ｅＣＨ２−ＣＣＩ工＋ ３８モル％
、結果を第１表に示す。(A): +CHL-CCI2+ 45 mol%
, -e-CH, -CH+45 mol% N (B): -eCH2-CCI + 38 mol%
, the results are shown in Table 1.
実施例５
塩化ビニリデン５０部（５２，９モル％）、メチルメタ
クリレ−）４０部（４１，１モル％）、Ｎ−フェニルマ
レイミド１０部（６，０モル％）、ジビニルベンゼン０
．０５部（０，０３８モル％）を実施例１と同様に反応
、処理した。Example 5 50 parts (52.9 mol%) of vinylidene chloride, 40 parts (41.1 mol%) of methyl methacrylate, 10 parts (6.0 mol%) of N-phenylmaleimide, 0 parts of divinylbenzene
．． 05 parts (0,038 mol %) were reacted and treated in the same manner as in Example 1.
重合率は９８％であった。得られた樹脂組成物のガラス
転移点は８５℃、可溶分のガラス転移点は８１℃、重量
平均分子量は１８０，０００であった。可溶分（Ａ）と
不溶分（Ｂ）の共重合体樹脂組成物の組成は以下の値で
あった。The polymerization rate was 98%. The resulting resin composition had a glass transition point of 85°C, a soluble component had a glass transition point of 81°C, and a weight average molecular weight of 180,000. The composition of the copolymer resin composition of soluble portion (A) and insoluble portion (B) was as follows.
（Ａ）二 千ＣＨ２−ＣＣｌ、＋ ５５モル％、Ｃ
Ｈ。(A) 2,000 CH2-CCl, +55 mol%, C
H.
−（−ＣＨ−ＣＨ＋−３９モル％ ０ ＝ Ｃ−ＯＣＨ。-(-CH-CH+-39 mol% 0 = C-OCH.
（Ｂ）： ＋ｃＨ，−Ｃｃｌエナ ５２モル％、
結果を第１表に示す。(B): +cH, -Ccl ena 52 mol%,
The results are shown in Table 1.
実施例６
塩化ビニリデン５０部（４１，２モル％）、Ｎ−２−ク
ロロフェニルマレイミド５部（２，０モル％）、アクリ
ロニトリル３０部（４５，２モル％）、スチレン１５部
（１），５モル％）、ジビニルベンゼン０．０４部（０
，０２５モル％）を実施例１と同様に反応、処理した。Example 6 50 parts of vinylidene chloride (41.2 mol%), 5 parts of N-2-chlorophenylmaleimide (2.0 mol%), 30 parts of acrylonitrile (45.2 mol%), 15 parts of styrene (1), 5 mol%), divinylbenzene 0.04 part (0
, 025 mol %) was reacted and treated in the same manner as in Example 1.
重合率は９７％であった。得られた樹脂組成物のガラス
転移点は１０１℃、可溶分のガラス転移点は８７℃、重
量平均分子量は２４２．０００であった。可溶分（Ａ）
と不溶分（Ｂ）の共重合体樹脂組成物の組成は以下の値
であった。The polymerization rate was 97%. The resulting resin composition had a glass transition point of 101°C, a soluble component had a glass transition point of 87°C, and a weight average molecular weight of 242.000. Soluble content (A)
The composition of the copolymer resin composition of and insoluble portion (B) was as follows.
（Ａ）： −＋ＣＨよ−ＣＣＩ□士 ４４モル％
、（Ｂ） ： ＋ＣＨ２−ＣＣＩＬ＋ ３９
モル％、結果を第１表に示す。(A): -+CH-CCI 44 mol%
, (B): +CH2-CCIL+ 39
The mol% results are shown in Table 1.
実施例７
塩化ヒニリデン５０部（４１，１モル％）、Ｎ−シクロ
へキシルマレイミド５部（２，２モル％）、アクリロニ
トリル３０部（４５，２モル％）、スチレン１５部（１
），５モル％）、ジビニルベンゼン０．０４部（０，０
２５モル％）を実施例１と同様に反応、処理した。Example 7 50 parts of hnylidene chloride (41.1 mol%), 5 parts of N-cyclohexylmaleimide (2.2 mol%), 30 parts of acrylonitrile (45.2 mol%), 15 parts of styrene (1
), 5 mol%), divinylbenzene 0.04 part (0,0
25 mol %) was reacted and treated in the same manner as in Example 1.
重合率は９７％であった。得られた樹脂組成物のガラス
転移点は９４℃、可溶分のガラス転移点は８２℃、重量
平均分子量は２４０，０００であった。可溶分（Ａ）と
不溶分（Ｂ）の共重合体樹脂組成物の組成は以下の値で
あった。The polymerization rate was 97%. The resulting resin composition had a glass transition point of 94°C, a soluble component had a glass transition point of 82°C, and a weight average molecular weight of 240,000. The composition of the copolymer resin composition of soluble portion (A) and insoluble portion (B) was as follows.
（Ａ）： 六℃Ｈｉ−ＣＣ１，−← ４５モル％、
［Ｆ］
→ＣＨ，−ＣＨ＋ ４５モル％Ｎ
（Ｂ）： ＋ＣＨ２，−ＣＣＩ汁 ３８モル％、
−＋ＣＨニーＣＨ＋ ４３モル％Ｎ
結果を第１表に示す。(A): 6°C Hi-CC1,-← 45 mol%,
[F] →CH, -CH+ 45 mol%N (B): +CH2, -CCI juice 38 mol%,
−+CHnee CH+ 43 mol%N The results are shown in Table 1.
実施例８
塩化ビニリデン５０部（４０，５モル％）、Ｎ−メチル
マレイミド５部（３，６モル％）、アクリロニトリル３
０部（４４，６モル％）、スチレン１５部（１），３モ
ル％）を実施例１と同様に反応、処理した。Example 8 50 parts of vinylidene chloride (40.5 mol%), 5 parts of N-methylmaleimide (3.6 mol%), 3 parts of acrylonitrile
0 parts (44.6 mol%) and 15 parts (1) of styrene (3 mol%) were reacted and treated in the same manner as in Example 1.
重合率は９７％であった。得られた樹脂組成物のガラス
転移点は９８℃、可溶分のガラス転移点は９０℃、重量
平均分子量は２２４．０００であった。可溶分（Ａ）と
不溶分（Ｂ）の共重合体樹脂組成物の組成は以下の値で
あった。The polymerization rate was 97%. The resulting resin composition had a glass transition point of 98°C, a soluble component had a glass transition point of 90°C, and a weight average molecular weight of 224.000. The composition of the copolymer resin composition of soluble portion (A) and insoluble portion (B) was as follows.
（Ａ）： →ＣＨニーＣＣＩＬ← ４５モル％、
Ｈ３
Ｎ
ＣＢ）： ＋ＣＨ２−ＣＣｌ、÷ ４０モル％、
【
Ｈ３
千ＣＨ，−ＣＨ← ０．０４モル％−←ＣＨ−Ｃ
Ｈ−一
結果を第１表に示す。(A): →CHnee CCIL← 45 mol%,
H3N CB): +CH2-CCl, ÷ 40 mol%,
[H3 1,000 CH, -CH← 0.04 mol% -←CH-C
H-1 results are shown in Table 1.
比較例１
塩化ヒニリデン５０部（４１，１モル％）、Ｎ−フェニ
ルマレイミド５部（２，４モル％）、アクリロニトリル
３０部（４５，１モル％）、スチレン１５部（１），４
モル％）を実施例１と同様に反応、処理した。Comparative Example 1 50 parts of hnylidene chloride (41.1 mol%), 5 parts of N-phenylmaleimide (2.4 mol%), 30 parts of acrylonitrile (45.1 mol%), 15 parts of styrene (1), 4
% by mole) was reacted and treated in the same manner as in Example 1.
得られた共重合体を実施例１と同様に発泡させたところ
、独立気泡率５０％の発泡体ができた。又実施例２と同
様に破断強度を測定したところ０．２０Ｋｇ／關てあっ
た。When the obtained copolymer was foamed in the same manner as in Example 1, a foam with a closed cell ratio of 50% was obtained. Moreover, when the breaking strength was measured in the same manner as in Example 2, it was found to be 0.20 kg/min.
比較例２
塩化ビニリデン５０部（５５，３モル％）、Ｎ−フェニ
ルマレイミド２０部（１２，５モル％）、メチルメタク
リレート３０部（３２，２モル％）を実施例１と同様に
反応、処理した。Comparative Example 2 50 parts (55.3 mol%) of vinylidene chloride, 20 parts (12.5 mol%) of N-phenylmaleimide, and 30 parts (32.2 mol%) of methyl methacrylate were reacted and treated in the same manner as in Example 1. did.
重合率は８７％であった。得られた共重合体樹脂組成物
には未反応のＮ−フェニルマレイミドが存在していた。The polymerization rate was 87%. Unreacted N-phenylmaleimide was present in the obtained copolymer resin composition.
結果を第１表に示す。The results are shown in Table 1.
第１表 （２）下余白）Table 1 (2) Bottom margin)
第１図は本発明の共重合体樹脂組成物の一例のＰＧＣチ
ャートである。第２図は本発明の共重合体樹脂組成物の
一例のＦＴ−ＩＲチャートである。FIG. 1 is a PGC chart of an example of the copolymer resin composition of the present invention. FIG. 2 is an FT-IR chart of an example of the copolymer resin composition of the present invention.
Claims (1)
構造単位からなり、その組成が（ａ）３０〜７０モル％
、（ｂ）１〜１０モル％、（ｃ）２５〜７０モル％であ
る共重合体で、その重量平均分子量が１０，０００〜６
００，０００で、ガラス転移点が８０℃以上のテトラヒ
ドロフランに可溶な成分（Ａ）と、下記の一般式（ａ）
、（ｂ）、（ｃ）、（ｄ）で表される構造単位からなり
、その組成が（ａ）２５〜６５モル％、（ｂ）１〜１０
モル％、（ｃ）２５〜７０モル％、（ｄ）０．０１〜０
．２モル％である共重合体で、テトラヒドロフランに不
溶な成分（Ｂ）とからなり、成分（Ａ）と（Ｂ）の配合
割合が、 （Ａ）＝１００−（Ｂ） １０重量％≦（Ｂ）≦８０重量％ であり、ガラス転移点が８５℃以上であることを特徴と
するハロゲン化ビニリデン系ランダム共重合体樹脂組成
物。 記 −（ＣＨ＿２−ＣＸ＿２）− （ａ） ▲数式、化学式、表等があります▼（ｂ） ▲数式、化学式、表等があります▼（ｃ） ▲数式、化学式、表等があります▼（ｄ） 〔但し、Ｘはハロゲン基、Ｒ＿１は炭素数１〜４のアル
キル基、シクロヘキシル基、フェニル基又は▲数式、化
学式、表等があります▼で表され、Ｒ＿６、Ｒ＿７は−
ＣＨ＿３、−Ｃ＿２Ｈ＿５、−Ｃｌ、−Ｂｒ、−ＯＣＨ
＿３、−Ｈを表し、Ｒ＿２、Ｒ＿４は−Ｈ、−ＣＨ＿３
を表し、Ｒ＿３はハロゲン基、−ＣＮ、▲数式、化学式
、表等があります▼、▲数式、化学式、表等があります
▼、−ＣＯＯＨ又は▲数式、化学式、表等があります▼ を表し、ｎ＝０〜８の整数で、Ｒ＿５はフェニレン基又
は▲数式、化学式、表等があります▼ 、−Ｏ−Ｃ＿ｋＨ＿２＿ｋＯ−（ｋは３〜６の整数）〕
。(1) Consisting of structural units represented by the following general formulas (a), (b), and (c), the composition of which is (a) 30 to 70 mol%
, (b) 1 to 10 mol%, and (c) 25 to 70 mol%, the weight average molecular weight of which is 10,000 to 6.
00,000, a component (A) soluble in tetrahydrofuran with a glass transition point of 80°C or higher, and the following general formula (a)
, (b), (c), and (d), the composition of which is (a) 25 to 65 mol%, (b) 1 to 10
Mol%, (c) 25-70 mol%, (d) 0.01-0
．． It is a copolymer with a content of 2 mol% and a component (B) insoluble in tetrahydrofuran, and the blending ratio of components (A) and (B) is (A) = 100 - (B) 10% by weight ≦ (B )≦80% by weight, and a glass transition point of 85° C. or higher. Note - (CH_2-CX_2) - (a) ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (b) ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (c) ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (d) [However, X is a halogen group, R_1 is an alkyl group having 1 to 4 carbon atoms, a cyclohexyl group, a phenyl group, or ▲There are mathematical formulas, chemical formulas, tables, etc.▼, and R_6 and R_7 are -
CH_3, -C_2H_5, -Cl, -Br, -OCH
_3, -H, R_2, R_4 are -H, -CH_3
, R_3 represents a halogen group, -CN, ▲There are mathematical formulas, chemical formulas, tables, etc.▼, ▲There are mathematical formulas, chemical formulas, tables, etc.▼, -COOH, or ▲There are mathematical formulas, chemical formulas, tables, etc.▼, and n = an integer from 0 to 8, R_5 is a phenylene group or ▲ has a mathematical formula, chemical formula, table, etc. ▼ , -O-C_kH_2_kO- (k is an integer from 3 to 6)]
.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP26933086A JPS63122745A (en) | 1986-11-12 | 1986-11-12 | Partially crosslinked vinylidene halide based copolymer resin composition |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP26933086A JPS63122745A (en) | 1986-11-12 | 1986-11-12 | Partially crosslinked vinylidene halide based copolymer resin composition |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS63122745A true JPS63122745A (en) | 1988-05-26 |
| JPH0588863B2 JPH0588863B2 (en) | 1993-12-24 |
Family
ID=17470858
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP26933086A Granted JPS63122745A (en) | 1986-11-12 | 1986-11-12 | Partially crosslinked vinylidene halide based copolymer resin composition |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS63122745A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO1994020572A1 (en) * | 1993-03-05 | 1994-09-15 | Asahi Kasei Kogyo Kabushiki Kaisha | Vinylidene chloride copolymer resin composition and monolayer film |
-
1986
- 1986-11-12 JP JP26933086A patent/JPS63122745A/en active Granted
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO1994020572A1 (en) * | 1993-03-05 | 1994-09-15 | Asahi Kasei Kogyo Kabushiki Kaisha | Vinylidene chloride copolymer resin composition and monolayer film |
| US5446101A (en) * | 1993-03-05 | 1995-08-29 | Asahi Kasei Kogyo Kabushiki Kaisha | Vinylidene chloride copolymer composition and monolayer film |
| CN1042440C (en) * | 1993-03-05 | 1999-03-10 | 旭化成工业株式会社 | Vinylidene chloride copolymer resin composition and monolayer film |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH0588863B2 (en) | 1993-12-24 |
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