NL8000355A - Werkwijze voor het bereiden van een polymeer van alfa-methylstyreen. - Google Patents

Werkwijze voor het bereiden van een polymeer van alfa-methylstyreen. Download PDF

Info

Publication number: NL8000355A
Authority: NL; Netherlands
Prior art keywords: methylstyrene; latex; softening agent; copolymer; polymer
Prior art date: 1980-01-19

Application number

NL8000355A

Other languages

English (en)

Dutch (nl)

Original Assignee

Stamicarbon

Priority date (The priority date 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 date listed.)

1980-01-19

Filing date

1980-01-19

Publication date

1981-08-17

1980-01-19 Application filed by Stamicarbon filed Critical Stamicarbon

1980-01-19 Priority to NL8000355A priority Critical patent/NL8000355A/nl

1980-12-19 Priority to US06/218,452 priority patent/US4340723A/en

1981-01-14 Priority to EP81200040A priority patent/EP0032769B1/en

1981-01-14 Priority to AT81200040T priority patent/ATE7147T1/de

1981-01-14 Priority to DE8181200040T priority patent/DE3163123D1/de

1981-01-16 Priority to JP489881A priority patent/JPS56104916A/ja

1981-01-16 Priority to ES498562A priority patent/ES498562A0/es

1981-01-19 Priority to DK22081A priority patent/DK22081A/da

1981-08-17 Publication of NL8000355A publication Critical patent/NL8000355A/nl

Links

229920000642 polymer Polymers 0.000 title claims description 25
238000004519 manufacturing process Methods 0.000 title claims description 5
229920000126 latex Polymers 0.000 claims abstract description 30
239000004816 latex Substances 0.000 claims abstract description 29
229920001577 copolymer Polymers 0.000 claims abstract description 26
XYLMUPLGERFSHI-UHFFFAOYSA-N alpha-Methylstyrene Chemical compound CC(=C)C1=CC=CC=C1 XYLMUPLGERFSHI-UHFFFAOYSA-N 0.000 claims abstract description 20
238000005345 coagulation Methods 0.000 claims abstract description 16
230000015271 coagulation Effects 0.000 claims abstract description 16
238000000034 method Methods 0.000 claims abstract description 15
NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 claims abstract description 11
PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims abstract description 10
239000000178 monomer Substances 0.000 claims abstract description 10
YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 39
239000004902 Softening Agent Substances 0.000 claims description 26
XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 12
238000009835 boiling Methods 0.000 claims description 11
238000001035 drying Methods 0.000 claims description 9
UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 6
150000001875 compounds Chemical class 0.000 claims description 6
229920001971 elastomer Polymers 0.000 claims description 5
238000006116 polymerization reaction Methods 0.000 claims description 5
239000005060 rubber Substances 0.000 claims description 5
239000000126 substance Substances 0.000 claims description 5
YNQLUTRBYVCPMQ-UHFFFAOYSA-N Ethylbenzene Chemical compound CCC1=CC=CC=C1 YNQLUTRBYVCPMQ-UHFFFAOYSA-N 0.000 claims description 4
-1 aliphatic chlorinated hydrocarbons Chemical class 0.000 claims description 3
XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 claims description 2
GYCMBHHDWRMZGG-UHFFFAOYSA-N Methylacrylonitrile Chemical compound CC(=C)C#N GYCMBHHDWRMZGG-UHFFFAOYSA-N 0.000 claims description 2
230000001112 coagulating effect Effects 0.000 claims description 2
VKEQBMCRQDSRET-UHFFFAOYSA-N Methylone Chemical compound CNC(C)C(=O)C1=CC=C2OCOC2=C1 VKEQBMCRQDSRET-UHFFFAOYSA-N 0.000 claims 1
125000005250 alkyl acrylate group Chemical group 0.000 claims 1
230000001804 emulsifying effect Effects 0.000 claims 1
239000002904 solvent Substances 0.000 claims 1
238000012545 processing Methods 0.000 abstract description 8
238000002360 preparation method Methods 0.000 abstract description 4
VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 abstract description 2
239000000843 powder Substances 0.000 description 8
239000003995 emulsifying agent Substances 0.000 description 7
ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 6
230000000052 comparative effect Effects 0.000 description 5
CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 4
239000002253 acid Substances 0.000 description 4
239000000839 emulsion Substances 0.000 description 4
239000008187 granular material Substances 0.000 description 4
238000000926 separation method Methods 0.000 description 4
JLBJTVDPSNHSKJ-UHFFFAOYSA-N 4-Methylstyrene Chemical compound CC1=CC=C(C=C)C=C1 JLBJTVDPSNHSKJ-UHFFFAOYSA-N 0.000 description 3
HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
125000004432 carbon atom Chemical group C* 0.000 description 3
238000001816 cooling Methods 0.000 description 3
239000003792 electrolyte Substances 0.000 description 3
NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical class OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
150000007513 acids Chemical class 0.000 description 2
ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 description 2
239000002245 particle Substances 0.000 description 2
239000004033 plastic Substances 0.000 description 2
229920003023 plastic Polymers 0.000 description 2
239000003505 polymerization initiator Substances 0.000 description 2
UOCLXMDMGBRAIB-UHFFFAOYSA-N 1,1,1-trichloroethane Chemical compound CC(Cl)(Cl)Cl UOCLXMDMGBRAIB-UHFFFAOYSA-N 0.000 description 1
JZHGRUMIRATHIU-UHFFFAOYSA-N 1-ethenyl-3-methylbenzene Chemical compound CC1=CC=CC(C=C)=C1 JZHGRUMIRATHIU-UHFFFAOYSA-N 0.000 description 1
OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 description 1
FRIBMENBGGCKPD-UHFFFAOYSA-N 3-(2,3-dimethoxyphenyl)prop-2-enal Chemical compound COC1=CC=CC(C=CC=O)=C1OC FRIBMENBGGCKPD-UHFFFAOYSA-N 0.000 description 1
BTXXTMOWISPQSJ-UHFFFAOYSA-N 4,4,4-trifluorobutan-2-one Chemical compound CC(=O)CC(F)(F)F BTXXTMOWISPQSJ-UHFFFAOYSA-N 0.000 description 1
BQACOLQNOUYJCE-FYZZASKESA-N Abietic acid Natural products CC(C)C1=CC2=CC[C@]3(C)[C@](C)(CCC[C@@]3(C)C(=O)O)[C@H]2CC1 BQACOLQNOUYJCE-FYZZASKESA-N 0.000 description 1
RSWGJHLUYNHPMX-UHFFFAOYSA-N Abietic-Saeure Natural products C12CCC(C(C)C)=CC2=CCC2C1(C)CCCC2(C)C(O)=O RSWGJHLUYNHPMX-UHFFFAOYSA-N 0.000 description 1
NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 1
UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 description 1
RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical class S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 description 1
229920002943 EPDM rubber Polymers 0.000 description 1
OTMSDBZUPAUEDD-UHFFFAOYSA-N Ethane Chemical compound CC OTMSDBZUPAUEDD-UHFFFAOYSA-N 0.000 description 1
JIGUQPWFLRLWPJ-UHFFFAOYSA-N Ethyl acrylate Chemical compound CCOC(=O)C=C JIGUQPWFLRLWPJ-UHFFFAOYSA-N 0.000 description 1
229920000181 Ethylene propylene rubber Polymers 0.000 description 1
229920000459 Nitrile rubber Polymers 0.000 description 1
CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
239000005062 Polybutadiene Substances 0.000 description 1
ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 description 1
230000002378 acidificating effect Effects 0.000 description 1
239000000654 additive Substances 0.000 description 1
150000008051 alkyl sulfates Chemical class 0.000 description 1
229940045714 alkyl sulfonate alkylating agent Drugs 0.000 description 1
150000008052 alkyl sulfonates Chemical class 0.000 description 1
229910001870 ammonium persulfate Inorganic materials 0.000 description 1
150000003863 ammonium salts Chemical class 0.000 description 1
125000000129 anionic group Chemical group 0.000 description 1
NTXGQCSETZTARF-UHFFFAOYSA-N buta-1,3-diene;prop-2-enenitrile Chemical compound C=CC=C.C=CC#N NTXGQCSETZTARF-UHFFFAOYSA-N 0.000 description 1
MTAZNLWOLGHBHU-UHFFFAOYSA-N butadiene-styrene rubber Chemical compound C=CC=C.C=CC1=CC=CC=C1 MTAZNLWOLGHBHU-UHFFFAOYSA-N 0.000 description 1
239000001110 calcium chloride Substances 0.000 description 1
229910001628 calcium chloride Inorganic materials 0.000 description 1
229950005499 carbon tetrachloride Drugs 0.000 description 1
125000002091 cationic group Chemical group 0.000 description 1
239000007795 chemical reaction product Substances 0.000 description 1
239000003153 chemical reaction reagent Substances 0.000 description 1
239000003638 chemical reducing agent Substances 0.000 description 1
239000003795 chemical substances by application Substances 0.000 description 1
238000011109 contamination Methods 0.000 description 1
235000014113 dietary fatty acids Nutrition 0.000 description 1
XPPKVPWEQAFLFU-UHFFFAOYSA-N diphosphoric acid Chemical class OP(O)(=O)OP(O)(O)=O XPPKVPWEQAFLFU-UHFFFAOYSA-N 0.000 description 1
WNAHIZMDSQCWRP-UHFFFAOYSA-N dodecane-1-thiol Chemical compound CCCCCCCCCCCCS WNAHIZMDSQCWRP-UHFFFAOYSA-N 0.000 description 1
238000007720 emulsion polymerization reaction Methods 0.000 description 1
239000000194 fatty acid Substances 0.000 description 1
229930195729 fatty acid Natural products 0.000 description 1
150000004665 fatty acids Chemical class 0.000 description 1
229940017705 formaldehyde sulfoxylate Drugs 0.000 description 1
238000007710 freezing Methods 0.000 description 1
230000008014 freezing Effects 0.000 description 1
SBGKURINHGJRFN-UHFFFAOYSA-N hydroxymethanesulfinic acid Chemical compound OCS(O)=O SBGKURINHGJRFN-UHFFFAOYSA-N 0.000 description 1
125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
KZCOBXFFBQJQHH-UHFFFAOYSA-N octane-1-thiol Chemical class CCCCCCCCS KZCOBXFFBQJQHH-UHFFFAOYSA-N 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
235000011007 phosphoric acid Nutrition 0.000 description 1
229920001084 poly(chloroprene) Polymers 0.000 description 1
229920002857 polybutadiene Polymers 0.000 description 1
239000011591 potassium Substances 0.000 description 1
159000000001 potassium salts Chemical class 0.000 description 1
229910052939 potassium sulfate Inorganic materials 0.000 description 1
239000000047 product Substances 0.000 description 1
229940005657 pyrophosphoric acid Drugs 0.000 description 1
239000011347 resin Chemical class 0.000 description 1
229920005989 resin Chemical class 0.000 description 1
150000003839 salts Chemical class 0.000 description 1
235000011121 sodium hydroxide Nutrition 0.000 description 1
159000000000 sodium salts Chemical class 0.000 description 1
239000011593 sulfur Substances 0.000 description 1
229910052717 sulfur Inorganic materials 0.000 description 1
VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 description 1
239000003021 water soluble solvent Substances 0.000 description 1
239000008096 xylene Substances 0.000 description 1

Classifications

- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F6/00—Post-polymerisation treatments
- C08F6/14—Treatment of polymer emulsions
- C08F6/22—Coagulation

Landscapes

Chemical & Material Sciences (AREA)
Health & Medical Sciences (AREA)
Chemical Kinetics & Catalysis (AREA)
Medicinal Chemistry (AREA)
Polymers & Plastics (AREA)
Organic Chemistry (AREA)
Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)

NL8000355A 1980-01-19 1980-01-19 Werkwijze voor het bereiden van een polymeer van alfa-methylstyreen. NL8000355A (nl)

Priority Applications (8)

Application Number	Priority Date	Filing Date	Title
NL8000355A NL8000355A (nl)	1980-01-19	1980-01-19	Werkwijze voor het bereiden van een polymeer van alfa-methylstyreen.
US06/218,452 US4340723A (en)	1980-01-19	1980-12-19	Process for the preparation of a copolymer of α-methylstyrene
EP81200040A EP0032769B1 (en)	1980-01-19	1981-01-14	Process for the preparation of a copolymer of alpha-methylstyrene
AT81200040T ATE7147T1 (de)	1980-01-19	1981-01-14	Verfahren zur herstellung eines copolymers aus alpha-methylstyrol.
DE8181200040T DE3163123D1 (en)	1980-01-19	1981-01-14	Process for the preparation of a copolymer of alpha-methylstyrene
JP489881A JPS56104916A (en)	1980-01-19	1981-01-16	Manufacture of alpha methylstyrene
ES498562A ES498562A0 (es)	1980-01-19	1981-01-16	Un procedimiento para la preparacion de copolimeros de a- metilestireno y uno o mas monomeros distintos
DK22081A DK22081A (da)	1980-01-19	1981-01-19	Fremgangsmaade til fremstilling af en copolymer af alfa-methylstyren

Applications Claiming Priority (2)

Application Number	Priority Date	Filing Date	Title
NL8000355		1980-01-19
NL8000355A NL8000355A (nl)	1980-01-19	1980-01-19	Werkwijze voor het bereiden van een polymeer van alfa-methylstyreen.

Publications (1)

Publication Number	Publication Date
NL8000355A true NL8000355A (nl)	1981-08-17

Family

ID=19834706

Family Applications (1)

Application Number	Title	Priority Date	Filing Date
NL8000355A NL8000355A (nl)	1980-01-19	1980-01-19	Werkwijze voor het bereiden van een polymeer van alfa-methylstyreen.

Country Status (8)

Country	Link
US (1)	US4340723A (da)
EP (1)	EP0032769B1 (da)
JP (1)	JPS56104916A (da)
AT (1)	ATE7147T1 (da)
DE (1)	DE3163123D1 (da)
DK (1)	DK22081A (da)
ES (1)	ES498562A0 (da)
NL (1)	NL8000355A (da)

Families Citing this family (8)

* Cited by examiner, † Cited by third party
Publication number	Priority date	Publication date	Assignee	Title
US4401806A (en) *	1981-01-27	1983-08-30	Kureha Kagaku Kogyo Kabushiki Kaisha	Process for producing graft copolymer
JPS5962604A (ja) *	1982-10-01	1984-04-10	Kanegafuchi Chem Ind Co Ltd	共重合体の製造方法
US4560735A (en) *	1984-03-29	1985-12-24	Kanegafuchi Kagaku Kogyo Kabushiki Kaisha	Process for preparing copolymer
DE3431194A1 (de) *	1984-08-24	1986-03-06	Bayer Ag, 5090 Leverkusen	Copolymerisate aus (delta)-methylstyrol und acrylnitril
JPH0653810B2 (ja) *	1985-08-21	1994-07-20	三菱レイヨン株式会社	粉粒状重合体およびその製造方法
CA1281454C (en) *	1985-12-25	1991-03-12	Teruhiko Sugimori	Method for producing thermoplastic resins
KR100417066B1 (ko) *	2001-01-08	2004-02-05	주식회사 엘지화학	내열성이 우수한 열가소성 수지의 제조방법
KR101706471B1 (ko)	2014-10-07	2017-02-13	주식회사 엘지화학	내열성 수지의 제조방법, 내열성 수지 및 내열 abs 수지 조성물

Family Cites Families (7)

* Cited by examiner, † Cited by third party
Publication number	Priority date	Publication date	Assignee	Title
BE587940A (da) *	1959-02-24
NL263649A (da) *	1960-04-15
NL149203B (nl) *	1967-10-20	1976-04-15	Goodrich Co B F	Werkwijze voor het bereiden van waterrijke suspensies van velvormende polymeerdeeltjes, alsmede de onder toepassing daarvan verkregen gevormde voortbrengselen.
GB1350777A (en) *	1970-10-08	1974-04-24	Kureha Chemical Ind Co Ltd	Method for coagulating rubber latex
US3875104A (en) *	1973-12-17	1975-04-01	American Cyanamid Co	Coagulation of oil-extended emulsions
CA1059696A (en) *	1975-03-20	1979-07-31	Polysar Limited	Latex coagulation process
US4001486A (en) *	1975-06-11	1977-01-04	Nalco Chemical Company	Latex coagulant for emulsion breakers

1980
- 1980-01-19 NL NL8000355A patent/NL8000355A/nl not_active Application Discontinuation
- 1980-12-19 US US06/218,452 patent/US4340723A/en not_active Expired - Fee Related
1981
- 1981-01-14 AT AT81200040T patent/ATE7147T1/de not_active IP Right Cessation
- 1981-01-14 EP EP81200040A patent/EP0032769B1/en not_active Expired
- 1981-01-14 DE DE8181200040T patent/DE3163123D1/de not_active Expired
- 1981-01-16 JP JP489881A patent/JPS56104916A/ja active Pending
- 1981-01-16 ES ES498562A patent/ES498562A0/es active Granted
- 1981-01-19 DK DK22081A patent/DK22081A/da not_active Application Discontinuation

Also Published As

Publication number	Publication date
ES8201182A1 (es)	1981-12-01
ATE7147T1 (de)	1984-05-15
US4340723A (en)	1982-07-20
EP0032769B1 (en)	1984-04-18
DE3163123D1 (en)	1984-05-24
DK22081A (da)	1981-07-20
ES498562A0 (es)	1981-12-01
EP0032769A1 (en)	1981-07-29
JPS56104916A (en)	1981-08-21

Legal Events

Date	Code	Title	Description
1981-08-17	A1B	A search report has been drawn up
1983-09-01	BV	The patent application has lapsed

Publication	Publication Date	Title
NL8000355A (nl)	1981-08-17	Werkwijze voor het bereiden van een polymeer van alfa-methylstyreen.
US4278582A (en)	1981-07-14	Removal of residual acrylonitrile monomer
US4623678A (en)	1986-11-18	Method for shear coagulation of latex resins
US4602083A (en)	1986-07-22	Coagulation process
US4412051A (en)	1983-10-25	Bromine-containing polymer and process of preparing a bromine-containing polymer
US5225465A (en)	1993-07-06	Process for working up stabilized abs polymers with recovery of unreacted monomers
CA1170399A (en)	1984-07-03	Process for the removal of residual monomers from abs polymers
JPS6219780B2 (da)	1987-05-01
US4690974A (en)	1987-09-01	Method for producing rubber modified thermoplastic resins
JPS638129B2 (da)	1988-02-20
US2643995A (en)	1953-06-30	Emulsion polymerization process
EP0119771B1 (en)	1988-08-03	Process for reducing the residual acrylonitrile monomer content of acrylonitrile copolymer resins
JPS61266417A (ja)	1986-11-26	水媒体中の遊離残留単量体の除去方法
JPS6219779B2 (da)	1987-05-01
US4764557A (en)	1988-08-16	Moulding compositions of uniform particle size and improved thermal stability
US5028349A (en)	1991-07-02	Moulding compositions having uniform particle size and improved thermal stability
US4690975A (en)	1987-09-01	Method for producing rubber modified thermoplastic resins
EP0044097B1 (en)	1985-04-03	Process for the preparation of a copolymer
WO1990013591A1 (en)	1990-11-15	Process for coagulating a grafted rubber compound
EP0009417B1 (en)	1982-12-15	A process for dewatering a grafted rubber latex
RU2779872C1 (ru)	2022-09-14	Способ прекращения радикальной полимеризации при синтезе эмульсионных бутадиен-стирольных каучуков
KR0178985B1 (ko)	1999-05-15	중합체에 결합된 작용기를 갖는 고무의 제조방법
JPH06107728A (ja)	1994-04-19	ブロモ化スチレン重合体粒子の製造方法
NL8004698A (nl)	1982-03-16	Werkwijze voor het bereiden van een copolymeer.
KR960000569B1 (ko)	1996-01-09	내충격성이 우수한 니트릴계 수지의 제조방법