JPH04261422A - Polyester compound and production thereof - Google Patents
Polyester compound and production thereofInfo
- Publication number
- JPH04261422A JPH04261422A JP2177891A JP2177891A JPH04261422A JP H04261422 A JPH04261422 A JP H04261422A JP 2177891 A JP2177891 A JP 2177891A JP 2177891 A JP2177891 A JP 2177891A JP H04261422 A JPH04261422 A JP H04261422A
- Authority
- JP
- Japan
- Prior art keywords
- formula
- sum
- chemical formula
- integer
- represent
- 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
- 150000001875 compounds Chemical class 0.000 title claims abstract description 26
- 229920000728 polyester Polymers 0.000 title claims abstract description 19
- 238000004519 manufacturing process Methods 0.000 title claims description 7
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 14
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims abstract description 9
- 239000000126 substance Substances 0.000 claims description 21
- 150000002148 esters Chemical class 0.000 claims description 10
- 229920005989 resin Polymers 0.000 abstract description 12
- 239000011347 resin Substances 0.000 abstract description 12
- 235000014113 dietary fatty acids Nutrition 0.000 abstract description 11
- 239000000194 fatty acid Substances 0.000 abstract description 11
- 229930195729 fatty acid Natural products 0.000 abstract description 11
- -1 hydroxy fatty acid Chemical class 0.000 abstract description 10
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 abstract description 9
- 230000006866 deterioration Effects 0.000 abstract description 8
- 230000000704 physical effect Effects 0.000 abstract description 7
- 238000000465 moulding Methods 0.000 abstract description 5
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 abstract description 4
- 229920001187 thermosetting polymer Polymers 0.000 abstract description 3
- 239000003795 chemical substances by application Substances 0.000 abstract 1
- 239000011248 coating agent Substances 0.000 abstract 1
- 238000000576 coating method Methods 0.000 abstract 1
- 238000006243 chemical reaction Methods 0.000 description 14
- 239000006082 mold release agent Substances 0.000 description 14
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 9
- ULQISTXYYBZJSJ-UHFFFAOYSA-N 12-hydroxyoctadecanoic acid Chemical compound CCCCCCC(O)CCCCCCCCCCC(O)=O ULQISTXYYBZJSJ-UHFFFAOYSA-N 0.000 description 6
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 description 6
- 238000009833 condensation Methods 0.000 description 5
- 230000005494 condensation Effects 0.000 description 5
- 229920001807 Urea-formaldehyde Polymers 0.000 description 4
- 239000003054 catalyst Substances 0.000 description 4
- 150000004665 fatty acids Chemical class 0.000 description 4
- XXMIOPMDWAUFGU-UHFFFAOYSA-N hexane-1,6-diol Chemical compound OCCCCCCO XXMIOPMDWAUFGU-UHFFFAOYSA-N 0.000 description 4
- 239000002994 raw material Substances 0.000 description 4
- 238000010992 reflux Methods 0.000 description 4
- 229940114072 12-hydroxystearic acid Drugs 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- FPCJKVGGYOAWIZ-UHFFFAOYSA-N butan-1-ol;titanium Chemical compound [Ti].CCCCO.CCCCO.CCCCO.CCCCO FPCJKVGGYOAWIZ-UHFFFAOYSA-N 0.000 description 3
- 238000011109 contamination Methods 0.000 description 3
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 3
- 150000004702 methyl esters Chemical class 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- PUPZLCDOIYMWBV-UHFFFAOYSA-N (+/-)-1,3-Butanediol Chemical compound CC(O)CCO PUPZLCDOIYMWBV-UHFFFAOYSA-N 0.000 description 2
- PAZZVPKITDJCPV-UHFFFAOYSA-N 10-hydroxyoctadecanoic acid Chemical compound CCCCCCCCC(O)CCCCCCCCC(O)=O PAZZVPKITDJCPV-UHFFFAOYSA-N 0.000 description 2
- YNQGVRJFSHTULP-UHFFFAOYSA-N 11-hydroxyhexadecanoic acid Chemical compound CCCCCC(O)CCCCCCCCCC(O)=O YNQGVRJFSHTULP-UHFFFAOYSA-N 0.000 description 2
- RKHXDCVAPIMDMG-UHFFFAOYSA-N 9-hydroxyoctadecanoic acid Chemical compound CCCCCCCCCC(O)CCCCCCCC(O)=O RKHXDCVAPIMDMG-UHFFFAOYSA-N 0.000 description 2
- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- AFVFQIVMOAPDHO-UHFFFAOYSA-N Methanesulfonic acid Chemical compound CS(O)(=O)=O AFVFQIVMOAPDHO-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- 235000021355 Stearic acid Nutrition 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000003822 epoxy resin Substances 0.000 description 2
- LNEPOXFFQSENCJ-UHFFFAOYSA-N haloperidol Chemical compound C1CC(O)(C=2C=CC(Cl)=CC=2)CCN1CCCC(=O)C1=CC=C(F)C=C1 LNEPOXFFQSENCJ-UHFFFAOYSA-N 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 2
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 description 2
- 229920001568 phenolic resin Polymers 0.000 description 2
- 239000005011 phenolic resin Substances 0.000 description 2
- 239000004014 plasticizer Substances 0.000 description 2
- 229920000647 polyepoxide Polymers 0.000 description 2
- 230000035484 reaction time Effects 0.000 description 2
- 239000008117 stearic acid Substances 0.000 description 2
- 229920002803 thermoplastic polyurethane Polymers 0.000 description 2
- 229920006337 unsaturated polyester resin Polymers 0.000 description 2
- DNIAPMSPPWPWGF-VKHMYHEASA-N (+)-propylene glycol Chemical compound C[C@H](O)CO DNIAPMSPPWPWGF-VKHMYHEASA-N 0.000 description 1
- DNIAPMSPPWPWGF-GSVOUGTGSA-N (R)-(-)-Propylene glycol Chemical compound C[C@@H](O)CO DNIAPMSPPWPWGF-GSVOUGTGSA-N 0.000 description 1
- YPFDHNVEDLHUCE-UHFFFAOYSA-N 1,3-propanediol Substances OCCCO YPFDHNVEDLHUCE-UHFFFAOYSA-N 0.000 description 1
- QUFMVAWAOYDYFV-UHFFFAOYSA-N 10-hydroxyhexadecanoic acid Chemical compound CCCCCCC(O)CCCCCCCCC(O)=O QUFMVAWAOYDYFV-UHFFFAOYSA-N 0.000 description 1
- CJUFNCPPYUSJPR-UHFFFAOYSA-N 11-Hydroxystearic acid Chemical compound CCCCCCCC(O)CCCCCCCCCC(O)=O CJUFNCPPYUSJPR-UHFFFAOYSA-N 0.000 description 1
- VXLJMBUCOXFMGJ-UHFFFAOYSA-N 12-hydroxyhexadecanoic acid Chemical compound CCCCC(O)CCCCCCCCCCC(O)=O VXLJMBUCOXFMGJ-UHFFFAOYSA-N 0.000 description 1
- LCZVSXRMYJUNFX-UHFFFAOYSA-N 2-[2-(2-hydroxypropoxy)propoxy]propan-1-ol Chemical compound CC(O)COC(C)COC(C)CO LCZVSXRMYJUNFX-UHFFFAOYSA-N 0.000 description 1
- KMEKMXBMYZGGDT-UHFFFAOYSA-N 8-hydroxyhexadecanoic acid Chemical compound CCCCCCCCC(O)CCCCCCC(O)=O KMEKMXBMYZGGDT-UHFFFAOYSA-N 0.000 description 1
- YYWHSFVJGXJTKD-UHFFFAOYSA-N 8-hydroxyoctadecanoic acid Chemical compound CCCCCCCCCCC(O)CCCCCCC(O)=O YYWHSFVJGXJTKD-UHFFFAOYSA-N 0.000 description 1
- LMLPQXIASCHLIF-UHFFFAOYSA-N 9-hydroxyhexadecanoic acid Chemical compound CCCCCCCC(O)CCCCCCCC(O)=O LMLPQXIASCHLIF-UHFFFAOYSA-N 0.000 description 1
- QVHMSMOUDQXMRS-UHFFFAOYSA-N PPG n4 Chemical compound CC(O)COC(C)COC(C)COC(C)CO QVHMSMOUDQXMRS-UHFFFAOYSA-N 0.000 description 1
- ALQSHHUCVQOPAS-UHFFFAOYSA-N Pentane-1,5-diol Chemical compound OCCCCCO ALQSHHUCVQOPAS-UHFFFAOYSA-N 0.000 description 1
- UWHCKJMYHZGTIT-UHFFFAOYSA-N Tetraethylene glycol, Natural products OCCOCCOCCOCCO UWHCKJMYHZGTIT-UHFFFAOYSA-N 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- BMRWNKZVCUKKSR-UHFFFAOYSA-N butane-1,2-diol Chemical compound CCC(O)CO BMRWNKZVCUKKSR-UHFFFAOYSA-N 0.000 description 1
- OWBTYPJTUOEWEK-UHFFFAOYSA-N butane-2,3-diol Chemical compound CC(O)C(C)O OWBTYPJTUOEWEK-UHFFFAOYSA-N 0.000 description 1
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 238000004440 column chromatography Methods 0.000 description 1
- 238000006482 condensation reaction Methods 0.000 description 1
- SZXQTJUDPRGNJN-UHFFFAOYSA-N dipropylene glycol Chemical compound OCCCOCCCO SZXQTJUDPRGNJN-UHFFFAOYSA-N 0.000 description 1
- 230000032050 esterification Effects 0.000 description 1
- 238000005886 esterification reaction Methods 0.000 description 1
- 125000004494 ethyl ester group Chemical group 0.000 description 1
- 150000002334 glycols Chemical class 0.000 description 1
- SXCBDZAEHILGLM-UHFFFAOYSA-N heptane-1,7-diol Chemical compound OCCCCCCCO SXCBDZAEHILGLM-UHFFFAOYSA-N 0.000 description 1
- 239000003456 ion exchange resin Substances 0.000 description 1
- 229920003303 ion-exchange polymer Polymers 0.000 description 1
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 1
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229940098779 methanesulfonic acid Drugs 0.000 description 1
- 238000000034 method Methods 0.000 description 1
- 150000007522 mineralic acids Chemical class 0.000 description 1
- 239000003607 modifier Substances 0.000 description 1
- DNIAPMSPPWPWGF-UHFFFAOYSA-N monopropylene glycol Natural products CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 1
- OEIJHBUUFURJLI-UHFFFAOYSA-N octane-1,8-diol Chemical compound OCCCCCCCCO OEIJHBUUFURJLI-UHFFFAOYSA-N 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- 235000005985 organic acids Nutrition 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 238000010422 painting Methods 0.000 description 1
- 229920000166 polytrimethylene carbonate Polymers 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 235000013772 propylene glycol Nutrition 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- ZIBGPFATKBEMQZ-UHFFFAOYSA-N triethylene glycol Chemical compound OCCOCCOCCO ZIBGPFATKBEMQZ-UHFFFAOYSA-N 0.000 description 1
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Polyesters Or Polycarbonates (AREA)
Abstract
Description
【0001】0001
【産業上の利用分野】本発明は、新規のポリエステル化
合物およびその製造方法に関する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a novel polyester compound and a method for producing the same.
【0002】これら一連の化合物は、例えば、不飽和ポ
リエステル樹脂、エポキシ樹脂、ウレタン/ウレア樹脂
、ウレア樹脂、フェノール樹脂等の一般の熱硬化型樹脂
の離型剤、可塑剤、改質剤等として使用できる。These series of compounds are used as mold release agents, plasticizers, modifiers, etc. for general thermosetting resins such as unsaturated polyester resins, epoxy resins, urethane/urea resins, urea resins, and phenolic resins. Can be used.
【0003】0003
【従来技術および問題点】一般に樹脂を成型する場合、
成型物が金型から容易に離型されることが重要である。
これらの目的を達成するために、種々の外部離型剤のみ
ならず、内部離型剤が開示されている。[Prior art and problems] Generally, when molding resin,
It is important that the molded product be easily released from the mold. To achieve these objectives, various external as well as internal mold release agents have been disclosed.
【0004】離型剤のなかで特に内部離型剤は、原料中
に相溶化し、硬化後の樹脂との相溶性が低い化合物が要
求される。このような化合物としては、通常、脂肪酸あ
るいはその金属塩等が使用されている。しかしながら、
このような作用の離型剤は、連続離型を行う際、金型内
に堆積し、成型品の表面の劣化をひきおこすため、定期
的に金型内の洗浄を行う必要がある。また、成型品の塗
装の前処理としておこなう有機溶剤洗浄により、離型剤
を樹脂表面から洗浄することが困難である。Among mold release agents, an internal mold release agent in particular is required to be a compound that is compatible with the raw material and has low compatibility with the cured resin. As such compounds, fatty acids or their metal salts are usually used. however,
A mold release agent having such an action accumulates in the mold during continuous mold release and causes deterioration of the surface of the molded product, so it is necessary to periodically clean the inside of the mold. Furthermore, it is difficult to wash the mold release agent from the resin surface by cleaning with an organic solvent as a pretreatment for painting the molded product.
【0005】一方、脂肪酸のエステル類も、内部離型剤
として使用されている。しかしながら、これらのエステ
ル類は一般に離型性に乏しく、また、離型性能を満足す
る量を添加すると、可塑剤として作用して成形物の物性
等の低下を招く。さらに、樹脂中にとりこまれたものが
、樹脂表面に徐々にしみだして塗装性を悪くする。On the other hand, esters of fatty acids have also been used as internal mold release agents. However, these esters generally have poor mold releasability, and if they are added in an amount that satisfies the mold release performance, they act as plasticizers and cause deterioration in the physical properties of the molded product. Furthermore, the substances trapped in the resin gradually seep out onto the resin surface, impairing paintability.
【0006】このように、現在使用されている内部離型
剤では、金型内の汚染、塗装性の劣化、成形物の物性の
低下等、種々の問題点を抱えている。[0006] As described above, the internal mold release agents currently in use have various problems such as contamination inside the mold, deterioration of paintability, and deterioration of the physical properties of molded products.
【0007】[0007]
【発明が解決しようとする課題】本発明者らは、前記し
たような離型剤としての問題点 ■金型内の汚染■塗
装性の劣化■成形物の物性の低下等を克服するために鋭
意検討した。[Problems to be Solved by the Invention] The present inventors have attempted to overcome the above-mentioned problems as a mold release agent, such as contamination in the mold, deterioration in paintability, and deterioration in the physical properties of molded products. I considered it carefully.
【0008】[0008]
【課題を解決するための手段】本発明者らは、上記の目
的を達成すべく鋭意検討した結果、本発明を完成するに
至った。[Means for Solving the Problems] The present inventors have completed the present invention as a result of intensive studies to achieve the above object.
【0009】すなわち、本発明は一般式(I)(化8)
That is, the present invention provides general formula (I) (chemical formula 8)
【0010】0010
【化8】
(式中m、nはその和が13または15である整数で、
r、sはそれぞれ0〜7の整数でかつその和が1〜7の
整数を表し、j、kはその和が1〜25である整数を表
し、R1 はHまたはC1 〜C4 のアルキル基を示
す。)または一般式(II)(化9)[Image Omitted] (In the formula, m and n are integers whose sum is 13 or 15,
r and s each represent an integer of 0 to 7 and the sum of the integers is 1 to 7, j and k represent an integer of the sum of 1 to 25, and R1 represents H or a C1 to C4 alkyl group. show. ) or general formula (II) (Chemical formula 9)
【0011】[0011]
【化9】
(式中m、nはその和が13または15である整数で、
tは1〜4の整数を表し、j、kはその和が1〜25で
ある整数を表し、R2 、R3 はHまたはC1 〜C
4 のアルキル基を示し、互いに同じであっても異なっ
てもよい。)で表されるポリエステル化合物および一般
式(III)(化10)[Image Omitted] (In the formula, m and n are integers whose sum is 13 or 15,
t represents an integer of 1 to 4, j and k represent integers whose sum is 1 to 25, R2 and R3 are H or C1 to C
4 represents an alkyl group, which may be the same or different from each other. ) and general formula (III) (Chemical formula 10)
【0012】0012
【化10】
(式中RはHまたはC1 〜C4 のアルキル基を示し
、m、nはその和が13または15である整数を示す。
)で表されるヒドロキシ脂肪酸またはそのエステルと一
般式(IV)(化11)(In the formula, R represents H or a C1 to C4 alkyl group, and m and n represent integers whose sum is 13 or 15.) and its ester and the general formula ( IV) (Chemical formula 11)
【0013】[0013]
【化11】
(式中r、sはそれぞれ0〜7の整数でかつその和が1
〜7の整数を表し、R1 はHまたはC1 〜C4 の
アルキル基を示す。)で表されるアルカンジオールまた
は一般式(V)(化12)[Chemical formula 11] (In the formula, r and s are each integers from 0 to 7, and the sum of them is 1
It represents an integer of ~7, and R1 represents H or a C1 to C4 alkyl group. ) or general formula (V) (Chemical formula 12)
【0014】[0014]
【化12】
(式中tは1〜4の整数を表し、R2 、R3 はHま
たはC1 〜C4 のアルキル基を示し、同じであって
も異なってもよい。)で表されるジオールとの反応によ
り製造される一般式(I)、(II)で表されるポリエ
ステル化合物の製造方法である。[Formula 12] (In the formula, t represents an integer of 1 to 4, R2 and R3 represent H or a C1 to C4 alkyl group, and may be the same or different.) This is a method for producing polyester compounds represented by general formulas (I) and (II) produced by reaction.
【0015】本発明のポリエステル化合物の特徴は、樹
脂成形時の離型剤として使用した場合、樹脂本来の物性
に影響を及ぼさずに、優れた離型性を示す。また、金型
の汚染、樹脂中からのしみだしによる塗装性の劣化等の
問題が生じない。A feature of the polyester compound of the present invention is that when used as a mold release agent during resin molding, it exhibits excellent mold release properties without affecting the inherent physical properties of the resin. Further, problems such as contamination of the mold and deterioration of paintability due to seepage from the resin do not occur.
【0016】以下、本発明のポリエステル化合物の具体
的な製造方法を示す。A specific method for producing the polyester compound of the present invention will be described below.
【0017】本発明のポリエステル化合物は、ヒドロキ
シ脂肪酸またはその低級アルコールエステルとグリコー
ルとの反応を行うことにより得られる。The polyester compound of the present invention can be obtained by reacting a hydroxy fatty acid or a lower alcohol ester thereof with a glycol.
【0018】本発明において、使用されるヒドロキシ脂
肪酸およびそのエステル類としては、8−ヒドロキシス
テアリン酸、9−ヒドロキシステアリン酸、10−ヒド
ロキシステアリン酸、11−ヒドロキシステアリン酸、
12−ヒドロキシステアリン酸、8−ヒドロキシパルミ
チン酸、9−ヒドロキシパルミチン酸、10−ヒドロキ
シパルミチン酸、11−ヒドロキシパルミチン酸、12
−ヒドロキシパルミチン酸、さらにはこれらのメチルエ
ステル、エチルエステル、プロピルエステル、イソプロ
ピルエステル、ブチルエステル、イソブチルエステル等
が使用できる。工業的には、これらの高純度品を使用す
る事は困難であり、通常、5〜15%原料由来のヒドキ
ロキシ基を持たない脂肪酸あるいはそのエステルを含有
した化合物を使用するが、反応および得られるポリエス
テル化合物には何ら影響を及ぼさない。In the present invention, the hydroxy fatty acids and esters thereof used include 8-hydroxystearic acid, 9-hydroxystearic acid, 10-hydroxystearic acid, 11-hydroxystearic acid,
12-hydroxystearic acid, 8-hydroxypalmitic acid, 9-hydroxypalmitic acid, 10-hydroxypalmitic acid, 11-hydroxypalmitic acid, 12
-Hydroxypalmitic acid, as well as their methyl esters, ethyl esters, propyl esters, isopropyl esters, butyl esters, isobutyl esters, etc. can be used. Industrially, it is difficult to use these high-purity products, and usually a compound containing 5 to 15% of a fatty acid or its ester that does not have a hydroxyl group derived from the raw material is used, but the It has no effect on polyester compounds.
【0019】また、使用されるグリコール類としては、
一般式(II)で表される化合物として1,2−エタン
ジオール、1,2−プロパンジオール、1,3−プロパ
ンジオール、1,2−ブタンジオール、1,3−ブタン
ジオール、1,4−ブタンジオール、1,5−ペンタン
ジオール、1,6−ヘキサンジオール、1,7−ヘプタ
ンジオール、1,8−オクタンジオール等が使用できる
。一般式(III)で表される化合物としては、2,3
−ブタンジオール、ジエチレングリコール、トリエチレ
ングリコール、テトラエチレングリコール、ジプロピレ
ングリコール、トリプロピレングリコール、テトラプロ
ピレングリコール等が使用できる。[0019] In addition, the glycols used include:
Compounds represented by general formula (II) include 1,2-ethanediol, 1,2-propanediol, 1,3-propanediol, 1,2-butanediol, 1,3-butanediol, 1,4- Butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,7-heptanediol, 1,8-octanediol, etc. can be used. As the compound represented by general formula (III), 2,3
-Butanediol, diethylene glycol, triethylene glycol, tetraethylene glycol, dipropylene glycol, tripropylene glycol, tetrapropylene glycol, etc. can be used.
【0020】反応に使用するヒドロキシ脂肪酸およびそ
のエステル100当量部に対して使用するグリコールは
、0〜30当量部がよい。このような組成で縮合反応を
行うと、最終的に平均分子量1000〜8000、ヒド
ロキシル数5〜70のポリエステル化合物が得られる。
ヒドロキシ脂肪酸中には、前述したように5〜15%程
度のヒドロキシ基を持たない脂肪酸が含まれており、そ
のものが縮合停止剤として働くため分子量は、8000
程度が限界である。ヒドロキシ脂肪酸あるいはそのエス
テルに対しグリコールのモル比が高いと分子量が増加せ
ず、結果として粘性が高く流動性が低いため、離型剤と
して使用する際原料への相溶性が悪く、原料の粘性が高
くなり成形性に支障をきたす。The amount of glycol used is preferably 0 to 30 parts by weight per 100 parts by weight of hydroxy fatty acid and its ester used in the reaction. When a condensation reaction is carried out with such a composition, a polyester compound having an average molecular weight of 1,000 to 8,000 and a hydroxyl number of 5 to 70 is finally obtained. As mentioned above, hydroxy fatty acids contain about 5 to 15% of fatty acids that do not have hydroxy groups, and because they act as condensation terminators, their molecular weight is 8,000.
The extent is the limit. If the molar ratio of glycol to hydroxy fatty acid or its ester is high, the molecular weight will not increase, resulting in high viscosity and low fluidity, so when used as a mold release agent, it will have poor compatibility with raw materials and the viscosity of raw materials will increase. It becomes high and interferes with moldability.
【0021】縮合を行う反応温度は特に制限はなく、1
00〜250℃、好ましくは170〜210℃でよい。
反応は、無触媒でも進行するが、触媒の添加により縮合
に要する反応時間を短縮することができる。The reaction temperature for condensation is not particularly limited;
The temperature may be 00 to 250°C, preferably 170 to 210°C. Although the reaction proceeds without a catalyst, the reaction time required for condensation can be shortened by adding a catalyst.
【0022】触媒としては、通常のエステル化触媒とし
て使われる硫酸、塩酸、リン酸等の無機酸、p−トルエ
ンスルホン酸、メタンスルホン酸等の有機酸、その他に
もアルコキシチタン、酸性イオン交換樹脂等が使用でき
る。Examples of catalysts include inorganic acids such as sulfuric acid, hydrochloric acid, and phosphoric acid, which are commonly used as esterification catalysts, organic acids such as p-toluenesulfonic acid and methanesulfonic acid, and alkoxy titanium and acidic ion exchange resins. etc. can be used.
【0023】また、反応は常圧でも進行するが、縮合に
より生じる水および低級アルコールを系中よりとりのぞ
く方が縮合時間を短縮できるので、減圧下に反応を行う
ことが望ましい。減圧度は、10〜100mmHg程度
でよい。Although the reaction proceeds under normal pressure, it is preferable to carry out the reaction under reduced pressure because the condensation time can be shortened by removing water and lower alcohols produced by the condensation from the system. The degree of pressure reduction may be about 10 to 100 mmHg.
【0024】反応時間は、反応温度、使用するヒドロキ
シ脂肪酸およびそのエステルの種類にもよるが20〜5
0時間で十分である。The reaction time varies from 20 to 50 minutes depending on the reaction temperature and the type of hydroxy fatty acid and its ester used.
0 hours is sufficient.
【0025】反応の終点は、ゲルカラムクロマトグラフ
ィーによる分子量の測定およびヒドロキシル価の測定に
より決定するこができる。反応終了後、得られたエステ
ル縮合物は、そのまま離型剤として使用できる。The end point of the reaction can be determined by measuring the molecular weight and hydroxyl value by gel column chromatography. After completion of the reaction, the obtained ester condensate can be used as it is as a mold release agent.
【0026】[0026]
【作用】このようにして得られる本発明のポリエステル
化合物は、樹脂成形時の離型剤として使用した場合、成
形品の物性、成形後の塗装性に影響を及ぼさずに、優れ
た離型性を与える。[Action] When the polyester compound of the present invention obtained in this way is used as a mold release agent during resin molding, it exhibits excellent mold release properties without affecting the physical properties of the molded product or the paintability after molding. give.
【0027】[0027]
【実施例】以下、実施例により本発明のポリエステル化
合物の合成法を詳細に説明するが、本発明はこれに限定
されるものではない。
実施例1
攪拌器、還流冷却器を備えた容器に12−ヒドロキシス
テアリン酸600g(純度87%、その他の主成分はス
テアリン酸)、メタノール1.3lおよびp−トルエン
スルホン酸3gを装入し、3時間還流を行った。反応終
了後、過剰のメタノールを留去し、残渣を温水(70〜
80℃)700mlで4回洗浄を行い、脱水してメチル
エステルを得た。これに、1,6−ヘキサンジオール3
3.7g、テトラブトキシチタン0.05mlを装入し
、190〜200℃の温度下、常圧で10時間、10〜
20mmHgで30時間反応を行い、ポリエステル化合
物を得た。EXAMPLES The method for synthesizing the polyester compound of the present invention will be explained in detail below using Examples, but the present invention is not limited thereto. Example 1 In a container equipped with a stirrer and a reflux condenser, 600 g of 12-hydroxystearic acid (purity 87%, other main components are stearic acid), 1.3 l of methanol, and 3 g of p-toluenesulfonic acid were charged, Reflux was performed for 3 hours. After the reaction is complete, excess methanol is distilled off and the residue is soaked in hot water (70~
The mixture was washed four times with 700 ml (80°C) and dehydrated to obtain methyl ester. To this, 1,6-hexanediol 3
3.7 g and 0.05 ml of tetrabutoxy titanium were charged and heated at a temperature of 190 to 200°C and normal pressure for 10 hours.
The reaction was carried out at 20 mmHg for 30 hours to obtain a polyester compound.
【0028】収量:590g
酸価:0.4
ヒドロキシル価:10
平均分子量:3000程度
実施例2
攪拌器、還流冷却器を備えた容器に12−ヒドロキシス
テアリン酸700g(純度87%、その他の主成分はス
テアリン酸)、1,6−ヘキサンジオール27.5g、
テトラブトキシチタン0.05mlを装入し、190〜
200℃の温度下、常圧で7時間、10〜20mmHg
で37時間反応を行い、ポリエステル化合物を得た。Yield: 590g Acid value: 0.4 Hydroxyl value: 10 Average molecular weight: about 3000 Example 2 700g of 12-hydroxystearic acid (purity 87%, other main components) was placed in a container equipped with a stirrer and reflux condenser. is stearic acid), 27.5 g of 1,6-hexanediol,
Charge 0.05ml of tetrabutoxy titanium and
10-20mmHg for 7 hours at a temperature of 200℃ and normal pressure
The reaction was carried out for 37 hours to obtain a polyester compound.
【0029】収量:670g
酸価:1.2
ヒドロキシル価:28.8
平均分子量:45000程度
実施例3
攪拌器、還流冷却器を備えた容器に9(10)−ヒドロ
キシステアリン酸515g、メタノール1.2lおよび
p−トルエンスルホン酸3gを装入し、3時間還流を行
った。反応終了後、過剰のメタノールを留去し、残渣を
温水(70〜80℃)700mlで4回洗浄を行い、脱
水してメチルエステルを得た。これに、1,6−ヘキサ
ンジオール33.7g、テトラブトキシチタン0.05
mlを装入し、190〜200℃の温度下、常圧で10
時間、10〜20mmHgで30時間反応を行い、ポリ
エステル化合物を得た。Yield: 670 g Acid value: 1.2 Hydroxyl value: 28.8 Average molecular weight: about 45,000 Example 3 In a container equipped with a stirrer and a reflux condenser, 515 g of 9(10)-hydroxystearic acid and 1. 2 liters and 3 g of p-toluenesulfonic acid were charged and refluxed for 3 hours. After the reaction was completed, excess methanol was distilled off, and the residue was washed four times with 700 ml of warm water (70 to 80°C) and dehydrated to obtain a methyl ester. To this, 33.7 g of 1,6-hexanediol, 0.05 g of tetrabutoxytitanium
ml at normal pressure at a temperature of 190 to 200°C.
The reaction was carried out for 30 hours at 10 to 20 mmHg to obtain a polyester compound.
【0030】収量:490g 酸価:0.7 ヒドロキシル価:15 平均分子量:3000程度Yield: 490g Acid value: 0.7 Hydroxyl value: 15 Average molecular weight: about 3000
【0031】[0031]
【発明の効果】本発明によれば、不飽和ポリエステル樹
脂、エポキシ樹脂、ウレタン/ウレア樹脂、ウレア樹脂
、フェノール樹脂等の一般の熱硬化型樹脂の離型剤とし
て使用した場合、物性、塗装性に影響を及ぼさずに、優
れた離型性を有する新規のポリエステル化合物およびそ
の製造方法を提供できる。Effects of the Invention According to the present invention, when used as a mold release agent for general thermosetting resins such as unsaturated polyester resins, epoxy resins, urethane/urea resins, urea resins, and phenolic resins, physical properties and paintability can be improved. It is possible to provide a novel polyester compound having excellent mold releasability without affecting the production of the same, and a method for producing the same.
Claims (3)
r、sはそれぞれ0〜7の整数でかつその和が1〜7の
整数を表し、j、kはその和が1〜25である整数を表
し、R1 はHまたはC1 〜C4 のアルキル基を示
す。)または一般式(II)(化2) 【化2】 (式中m、nはその和が13または15である整数で、
tは1〜4の整数を表し、j、kはその和が1〜25で
ある整数を表し、R2 、R3 はHまたはC1 〜C
4 のアルキル基を示し、互いに同じであっても異なっ
てもよい。)で表されるポリエステル化合物。Claim 1: General formula (I) (Chemical formula 1) [Chemical formula 1] (In the formula, m and n are integers whose sum is 13 or 15,
r and s each represent an integer of 0 to 7 and the sum of the integers is 1 to 7, j and k represent an integer of the sum of 1 to 25, and R1 represents H or a C1 to C4 alkyl group. show. ) or general formula (II) (Chemical formula 2) [Chemical formula 2] (In the formula, m and n are integers whose sum is 13 or 15,
t represents an integer of 1 to 4, j and k represent integers whose sum is 1 to 25, R2 and R3 are H or C1 to C
4 represents an alkyl group, which may be the same or different from each other. ) A polyester compound represented by
ドロキシ数が5〜70であることを特徴とする請求項1
記載のポリエステル化合物。Claim 2: Claim 1, characterized in that the average molecular weight is 1000 to 8000 and the hydroxy number is 5 to 70.
The polyester compound described.
、m、nはその和が13または15である整数を示す。 )で表されるヒドロキシ脂肪酸またはそのエステルと一
般式(IV)(化4) 【化4】 (式中r、sはそれぞれ0〜7の整数でかつその和が1
〜7の整数を表し、R1 はHまたはC1 〜C4 の
アルキル基を示す。)で表されるアルカンジオールまた
は一般式(V)(化5) 【化5】 (式中tは1〜4の整数を表し、R2 、R3 はHま
たはC1 〜C4 のアルキル基を示し、同じであって
も異なってもよい。)で表されるジオールとの反応によ
り合成することを特徴とする一般式(I)(化6)【化
6】 (式中m、nはその和が13または15である整数で、
r、sはそれぞれ0〜7の整数でかつその和が1〜7の
整数を表し、j、kはその和が1〜25である整数を表
し、R1 はHまたはC1 〜C4 のアルキル基を示
す。)または一般式(II)(化7) 【化7】 (式中m、nはその和が13または15である整数で、
tは1〜4の整数を表し、j、kはその和が1〜25で
ある整数を表し、R2 、R3 はHまたはC1 〜C
4 のアルキル基を示し、互いに同じであっても異なっ
てもよい。)で表されるポリエステル化合物の製造方法
。3. General formula (III) (Chemical formula 3) [Chemical formula 3] (In the formula, R represents H or a C1 to C4 alkyl group, and m and n represent integers whose sum is 13 or 15. ) or its ester and the general formula (IV) (Chemical formula 4) [Chemical formula 4] (In the formula, r and s are each an integer of 0 to 7, and the sum thereof is 1.
It represents an integer of ~7, and R1 represents H or a C1 to C4 alkyl group. ) or an alkanediol represented by the general formula (V) (Chemical formula 5) [Chemical formula 5] (In the formula, t represents an integer of 1 to 4, R2 and R3 represent H or a C1 to C4 alkyl group, and the same General formula (I) (Chemical formula 6) [Chemical formula 6] (In the formula, m and n have a sum of 13 or an integer that is 15,
r and s each represent an integer of 0 to 7 and the sum of the integers is 1 to 7, j and k represent an integer of the sum of 1 to 25, and R1 represents H or a C1 to C4 alkyl group. show. ) or general formula (II) (Chemical formula 7) [Chemical formula 7] (In the formula, m and n are integers whose sum is 13 or 15,
t represents an integer of 1 to 4, j and k represent integers whose sum is 1 to 25, R2 and R3 are H or C1 to C
4 represents an alkyl group, which may be the same or different from each other. ) A method for producing a polyester compound represented by
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP2177891A JP2863329B2 (en) | 1991-02-15 | 1991-02-15 | Polyester compound and method for producing the same |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP2177891A JP2863329B2 (en) | 1991-02-15 | 1991-02-15 | Polyester compound and method for producing the same |
Publications (2)
Publication Number | Publication Date |
---|---|
JPH04261422A true JPH04261422A (en) | 1992-09-17 |
JP2863329B2 JP2863329B2 (en) | 1999-03-03 |
Family
ID=12064519
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JP2177891A Expired - Fee Related JP2863329B2 (en) | 1991-02-15 | 1991-02-15 | Polyester compound and method for producing the same |
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Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2012532956A (en) * | 2009-07-10 | 2012-12-20 | ダウ グローバル テクノロジーズ エルエルシー | Esters of secondary hydroxy fatty acid oligomers and their production |
-
1991
- 1991-02-15 JP JP2177891A patent/JP2863329B2/en not_active Expired - Fee Related
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2012532956A (en) * | 2009-07-10 | 2012-12-20 | ダウ グローバル テクノロジーズ エルエルシー | Esters of secondary hydroxy fatty acid oligomers and their production |
Also Published As
Publication number | Publication date |
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JP2863329B2 (en) | 1999-03-03 |
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