JPH0248551A - (meth)acrylic ester mixture - Google Patents
(meth)acrylic ester mixtureInfo
- Publication number
- JPH0248551A JPH0248551A JP19724888A JP19724888A JPH0248551A JP H0248551 A JPH0248551 A JP H0248551A JP 19724888 A JP19724888 A JP 19724888A JP 19724888 A JP19724888 A JP 19724888A JP H0248551 A JPH0248551 A JP H0248551A
- Authority
- JP
- Japan
- Prior art keywords
- meth
- mixture
- caprolactone
- tripentaerythritol
- acrylic acid
- 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.)
- Pending
Links
- 239000000203 mixture Substances 0.000 title claims abstract description 26
- -1 acrylic ester Chemical class 0.000 title abstract description 10
- PAPBSGBWRJIAAV-UHFFFAOYSA-N ε-Caprolactone Chemical compound O=C1CCCCCO1 PAPBSGBWRJIAAV-UHFFFAOYSA-N 0.000 claims abstract description 18
- PTJWCLYPVFJWMP-UHFFFAOYSA-N 2-[[3-hydroxy-2-[[3-hydroxy-2,2-bis(hydroxymethyl)propoxy]methyl]-2-(hydroxymethyl)propoxy]methyl]-2-(hydroxymethyl)propane-1,3-diol Chemical compound OCC(CO)(CO)COCC(CO)(CO)COCC(CO)(CO)CO PTJWCLYPVFJWMP-UHFFFAOYSA-N 0.000 claims abstract description 17
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 claims abstract description 16
- 239000007795 chemical reaction product Substances 0.000 claims abstract description 11
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 abstract description 10
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 abstract description 7
- 239000000463 material Substances 0.000 abstract description 7
- 230000005855 radiation Effects 0.000 abstract description 7
- 238000000576 coating method Methods 0.000 abstract description 6
- 238000001723 curing Methods 0.000 abstract description 6
- 239000011248 coating agent Substances 0.000 abstract description 5
- 239000003999 initiator Substances 0.000 abstract description 4
- 150000001875 compounds Chemical class 0.000 abstract description 3
- 239000003085 diluting agent Substances 0.000 abstract description 3
- 238000003847 radiation curing Methods 0.000 abstract description 3
- 238000006243 chemical reaction Methods 0.000 description 18
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 11
- 239000000126 substance Substances 0.000 description 10
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 9
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 9
- 239000002904 solvent Substances 0.000 description 8
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 description 6
- 238000005481 NMR spectroscopy Methods 0.000 description 6
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 6
- TXUICONDJPYNPY-UHFFFAOYSA-N (1,10,13-trimethyl-3-oxo-4,5,6,7,8,9,11,12,14,15,16,17-dodecahydrocyclopenta[a]phenanthren-17-yl) heptanoate Chemical compound C1CC2CC(=O)C=C(C)C2(C)C2C1C1CCC(OC(=O)CCCCCC)C1(C)CC2 TXUICONDJPYNPY-UHFFFAOYSA-N 0.000 description 5
- 229910021626 Tin(II) chloride Inorganic materials 0.000 description 5
- 239000003054 catalyst Substances 0.000 description 5
- 239000001119 stannous chloride Substances 0.000 description 5
- 235000011150 stannous chloride Nutrition 0.000 description 5
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 4
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 4
- 238000005259 measurement Methods 0.000 description 4
- 238000000034 method Methods 0.000 description 4
- 238000006116 polymerization reaction Methods 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 description 4
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 3
- 238000010521 absorption reaction Methods 0.000 description 3
- 239000003112 inhibitor Substances 0.000 description 3
- 239000000976 ink Substances 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 description 3
- 239000011541 reaction mixture Substances 0.000 description 3
- 235000011121 sodium hydroxide Nutrition 0.000 description 3
- AZQWKYJCGOJGHM-UHFFFAOYSA-N 1,4-benzoquinone Chemical compound O=C1C=CC(=O)C=C1 AZQWKYJCGOJGHM-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 2
- 239000013256 coordination polymer Substances 0.000 description 2
- 238000005336 cracking Methods 0.000 description 2
- 238000010894 electron beam technology Methods 0.000 description 2
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 2
- 230000003472 neutralizing effect Effects 0.000 description 2
- 239000003973 paint Substances 0.000 description 2
- VXUYXOFXAQZZMF-UHFFFAOYSA-N titanium(IV) isopropoxide Chemical compound CC(C)O[Ti](OC(C)C)(OC(C)C)OC(C)C VXUYXOFXAQZZMF-UHFFFAOYSA-N 0.000 description 2
- YXAOOTNFFAQIPZ-UHFFFAOYSA-N 1-nitrosonaphthalen-2-ol Chemical compound C1=CC=CC2=C(N=O)C(O)=CC=C21 YXAOOTNFFAQIPZ-UHFFFAOYSA-N 0.000 description 1
- WJFKNYWRSNBZNX-UHFFFAOYSA-N 10H-phenothiazine Chemical compound C1=CC=C2NC3=CC=CC=C3SC2=C1 WJFKNYWRSNBZNX-UHFFFAOYSA-N 0.000 description 1
- OPLCSTZDXXUYDU-UHFFFAOYSA-N 2,4-dimethyl-6-tert-butylphenol Chemical compound CC1=CC(C)=C(O)C(C(C)(C)C)=C1 OPLCSTZDXXUYDU-UHFFFAOYSA-N 0.000 description 1
- QFSYADJLNBHAKO-UHFFFAOYSA-N 2,5-dihydroxy-1,4-benzoquinone Chemical compound OC1=CC(=O)C(O)=CC1=O QFSYADJLNBHAKO-UHFFFAOYSA-N 0.000 description 1
- TXBCBTDQIULDIA-UHFFFAOYSA-N 2-[[3-hydroxy-2,2-bis(hydroxymethyl)propoxy]methyl]-2-(hydroxymethyl)propane-1,3-diol Chemical compound OCC(CO)(CO)COCC(CO)(CO)CO TXBCBTDQIULDIA-UHFFFAOYSA-N 0.000 description 1
- 239000004386 Erythritol Substances 0.000 description 1
- UNXHWFMMPAWVPI-UHFFFAOYSA-N Erythritol Natural products OCC(O)C(O)CO UNXHWFMMPAWVPI-UHFFFAOYSA-N 0.000 description 1
- UBUCNCOMADRQHX-UHFFFAOYSA-N N-Nitrosodiphenylamine Chemical compound C=1C=CC=CC=1N(N=O)C1=CC=CC=C1 UBUCNCOMADRQHX-UHFFFAOYSA-N 0.000 description 1
- 239000002202 Polyethylene glycol Substances 0.000 description 1
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 description 1
- 230000005856 abnormality Effects 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 150000001338 aliphatic hydrocarbons Chemical class 0.000 description 1
- 239000012670 alkaline solution Substances 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- YHWCPXVTRSHPNY-UHFFFAOYSA-N butan-1-olate;titanium(4+) Chemical compound [Ti+4].CCCC[O-].CCCC[O-].CCCC[O-].CCCC[O-] YHWCPXVTRSHPNY-UHFFFAOYSA-N 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 150000001879 copper Chemical class 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000012776 electronic material Substances 0.000 description 1
- UNXHWFMMPAWVPI-ZXZARUISSA-N erythritol Chemical compound OC[C@H](O)[C@H](O)CO UNXHWFMMPAWVPI-ZXZARUISSA-N 0.000 description 1
- 229940009714 erythritol Drugs 0.000 description 1
- 235000019414 erythritol Nutrition 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 238000013007 heat curing Methods 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 150000001451 organic peroxides Chemical class 0.000 description 1
- NWVVVBRKAWDGAB-UHFFFAOYSA-N p-methoxyphenol Chemical compound COC1=CC=C(O)C=C1 NWVVVBRKAWDGAB-UHFFFAOYSA-N 0.000 description 1
- 229950000688 phenothiazine Drugs 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 239000013558 reference substance Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 238000004904 shortening Methods 0.000 description 1
- CZDYPVPMEAXLPK-UHFFFAOYSA-N tetramethylsilane Chemical compound C[Si](C)(C)C CZDYPVPMEAXLPK-UHFFFAOYSA-N 0.000 description 1
- CRHIAMBJMSSNNM-UHFFFAOYSA-N tetraphenylstannane Chemical compound C1=CC=CC=C1[Sn](C=1C=CC=CC=1)(C=1C=CC=CC=1)C1=CC=CC=C1 CRHIAMBJMSSNNM-UHFFFAOYSA-N 0.000 description 1
- 150000003606 tin compounds Chemical class 0.000 description 1
- 150000003609 titanium compounds Chemical class 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Polyesters Or Polycarbonates (AREA)
Abstract
Description
【発明の詳細な説明】
(産業上の利用分野)
本発明は、熱紫外線、放射線、ラジカル開始剤の存在下
で容易に重合しうる新規な(メタ)アクリル酸エステル
混合物に関するものである。DETAILED DESCRIPTION OF THE INVENTION (Industrial Application Field) The present invention relates to a novel (meth)acrylic acid ester mixture that can be easily polymerized in the presence of hot ultraviolet light, radiation, or a radical initiator.
(従来の技術)
従来よりよく知られている多官能性(メタ)アクリル酸
エステルとしては、例えば名オペンチルグリコールジ(
メタ)アクリレート、1.6−ヘキサンシオールジ(メ
タ)アクリレート、ポリエチレングリコールジ(メタ)
アクリレート、ビスフェノールAジオキシエチルエーテ
ルジ(メタ)アクリレート、トリメチロールプロパント
リ (メタ)アクリレート、ペンタエリスリトールトリ
(メタ)アクリレート、ペンタエリスリトールテトラ
(メタ)アクリレート、ジペンタエリスリトールペンタ
(メタ)アクリレート、ジペンタエリスリトルへキサ(
メタ)アクリレート等が挙げられる。(Prior Art) As a conventionally well-known polyfunctional (meth)acrylic acid ester, for example, the name opentyl glycol di(
meth)acrylate, 1,6-hexanethiol di(meth)acrylate, polyethylene glycol di(meth)
Acrylate, bisphenol A dioxyethyl ether di(meth)acrylate, trimethylolpropane tri(meth)acrylate, pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, dipentaerythritol penta(meth)acrylate, dipenta Ellis Little Hexa (
Examples include meth)acrylate.
(発明が解決しようとする課題)
これ等の多官能性(メタ)アクリル酸エステルは、紫外
線硬化型あるいは電子線硬化型の樹脂として2ポ4や紫
外線硬化性のインクのビヒクルとして用いられている。(Problems to be Solved by the Invention) These polyfunctional (meth)acrylic esters are used as UV-curable or electron beam-curable resins as vehicles for 2PO4 and UV-curable inks. .
これ等の多官能性(メタ)アクリル酸エステルのうち、
硬化塗膜の硬度の大きいものとしては、ペンタエリスリ
トールテトラ(メタ)アクリレート、ジベンタエIJス
ルトールヘキサ(メタ)アクリレート等がある。しかし
更に高硬度のものが求められており、又これ等のものは
常温でワックス状であワたり、粘度が高く取扱いにくい
という欠点がある。Among these polyfunctional (meth)acrylic esters,
Examples of cured coatings with high hardness include pentaerythritol tetra(meth)acrylate and diventae IJ sultol hexa(meth)acrylate. However, there is a demand for materials with even higher hardness, and these materials have the drawbacks of being waxy and hot at room temperature, having a high viscosity, and being difficult to handle.
(課題を解決するための手段)
本発明は、紫外線硬化型あるいは電子線硬化型印刷イン
キ及び塗料の希釈剤として特にを用な低粘度の硬化性の
優れた新規な(メタ)アクリル酸エステル混合物を提供
することにある。更に一般に高硬度の硬化塗膜を与える
ものは脆いという欠点があり、軟らかい硬化塗膜を与え
るものは、官能基数が少ないため、硬化速度が遅いとい
う欠点がある。ところが本発明が提供する新規な(メタ
)アクリル酸エステル混合物は、従来知られている(メ
タ)アクリル酸エステルよりも柔軟性があり、かつ高硬
度の塗膜を与え、しかも硬化性が非常に優れている。す
なわら、本発明は、トリペンタエリスリトール及び/又
はテトラペンタエリスリトルとε−カプロラクトンの反
応物の(メタ)アクリル酸エステル混合物に関するもの
である。(Means for Solving the Problems) The present invention provides a novel (meth)acrylic acid ester mixture with low viscosity and excellent curability, which is particularly useful as a diluent for ultraviolet curable or electron beam curable printing inks and paints. Our goal is to provide the following. Furthermore, those that give a highly hard cured coating film generally have the disadvantage of being brittle, and those that give a soft cured coating film have a disadvantage of slow curing speed because they have a small number of functional groups. However, the novel (meth)acrylic ester mixture provided by the present invention is more flexible than the conventionally known (meth)acrylic esters, provides a coating film with high hardness, and has extremely high curability. Are better. Specifically, the present invention relates to a (meth)acrylic acid ester mixture of a reaction product of tripentaerythritol and/or tetrapentaerythritol and ε-caprolactone.
この新規な(メタ)アクリル酸エステル混合物は、トリ
ペンタエリスリトール及び/又はテトラペンタエリスリ
トールとε−カプロラクトンの反応物とアクリル酸また
はメタクリル酸又はその混合物との反応により製造する
ことができる。トリペンタエリスリトール及び/又はテ
トラペンタエリスリトールの1水酸基当量に対して、ε
−カプロラクトンの使用量は好ましくは0.1〜5化学
当量であるが、特に好ましくは0.5〜2.0化学当量
である。This novel (meth)acrylic acid ester mixture can be prepared by reacting a reaction product of tripentaerythritol and/or tetrapentaerythritol with ε-caprolactone and acrylic acid or methacrylic acid or a mixture thereof. For one hydroxyl group equivalent of tripentaerythritol and/or tetrapentaerythritol, ε
- The amount of caprolactone used is preferably 0.1 to 5 chemical equivalents, particularly preferably 0.5 to 2.0 chemical equivalents.
反応は、触媒を使用し、不活性ガス(例えば、窒素、炭
酸ガス等)雰囲気下で行うのが好ましい。The reaction is preferably carried out using a catalyst under an inert gas (eg, nitrogen, carbon dioxide, etc.) atmosphere.
触媒の具体的な例として、テトライソプロピルチタネー
ト、テトラブチルチタネート等の有機チタン化合物、テ
トラフェニルすず、ジラウリルすずオキサイド、塩化第
1すす等のすず化合物などを挙げることができる。Specific examples of the catalyst include organic titanium compounds such as tetraisopropyl titanate and tetrabutyl titanate, and tin compounds such as tetraphenyltin, dilauryltin oxide, and stannous chloride.
その使用量は、ε−カプロラクトンの重量を基準にして
好ましくは、0.0001−1.0重量%、特に好まし
くは0.01−0.2重量%である。The amount used is preferably 0.0001-1.0% by weight, particularly preferably 0.01-0.2% by weight, based on the weight of ε-caprolactone.
反応温度は、50〜300℃の範囲でよいが、好ましく
は100〜200 ℃で行うのが良い。The reaction temperature may be in the range of 50 to 300°C, preferably 100 to 200°C.
トリペンタエリスリトール及び/又はテトラペンタエリ
スリトールとξ−カプロラクトンの反応物の1水酸基当
量に対するアクリル酸又はメタクリル酸の使用量は、通
常1〜2.0化学当量であるが、好ましくは1.1〜1
.5化学当量である。The amount of acrylic acid or methacrylic acid used per 1 hydroxyl group equivalent of the reaction product of tripentaerythritol and/or tetrapentaerythritol and ξ-caprolactone is usually 1 to 2.0 chemical equivalents, preferably 1.1 to 1.
.. 5 chemical equivalents.
反応は、触媒を使用し、生成する水は留去する事により
促進される。このような触媒は、硫酸、Pトルエンスル
ホン酸等の酸性触媒であり、その使用量は、アクリル酸
またはメタクリル酸に対して通常0.1−1oモル%、
好ましくは1〜5モル%使用される。反応により生成し
た水を留去するには共沸溶剤を用いるのが有利である。The reaction is accelerated by using a catalyst and by distilling off the water produced. Such catalysts are acidic catalysts such as sulfuric acid and P-toluenesulfonic acid, and the amount used is usually 0.1-10 mol%, based on acrylic acid or methacrylic acid.
Preferably it is used in an amount of 1 to 5 mol%. It is advantageous to use an azeotropic solvent to distill off the water produced by the reaction.
このような共沸溶剤は、60〜150℃の沸点を有し、
水と分離し易いものならば使用出来るが、n−ヘキサン
、n−へブタンのような脂肪族炭化水素、ヘンゼン、ト
ルエンのような芳香族炭化水素、シクロヘキサンのよう
な脂環式炭化水素が適している。その使用量は通常、反
応混合物の5〜70重量%である。Such azeotropic solvents have a boiling point of 60-150°C,
Any substance that can be easily separated from water can be used, but aliphatic hydrocarbons such as n-hexane and n-hebutane, aromatic hydrocarbons such as henzene and toluene, and alicyclic hydrocarbons such as cyclohexane are suitable. ing. The amount used is usually 5-70% by weight of the reaction mixture.
反応温度は、60〜150 ℃の範囲でよいが、反応時
間の短縮と重合防止の点から、75〜120℃で行われ
るのが有利である。アクリル酸またはメタクリル酸には
既に重合防止剤が、添加されているのが普通であるが、
反応時に改めて重合防止剤を添加しても良い、そのよう
な重合防止剤には、ハイドロキノン、P−メトキシフェ
ノール、2.4−ジメチル−6−ターシャリ−ブチルフ
ェノール、α−ニトロソ−β−ナフトール、P−ベンゾ
キノン、2.5−ジヒドロキシ−P−キノン、フェノチ
アジン、N−ニトロソジフェニルアミン、銅塩等が挙げ
られる。その使用量は、通常反応混合物に対して0.0
1〜1重量%である。このようにして得られた本発明の
(メタ)アクリル酸エステル混合物は、必要ならば、水
あるいはアルカリ水溶液等で洗浄したり残圧蒸留のよう
な方法で溶剤と分離する事によって、工業的用途に使用
される。この(メタ)アクリル酸エステル混合物は、塗
料、ハードコート、インキ組成物及びエレクトロニクス
用材料として有用であり、それらは、放射線により、ま
たは、熱的な手段により硬化させる事が出来る。放射線
硬化は、イオン化もびくは電子線のような微粒子放射に
より、または紫外線放射のような化学線により行うこと
が出来る。化学線により硬化を行う場合には、−船釣に
当業界に公知の多くの種類の光重合開始剤を包含させる
。放射線硬化技術及び熱硬化技術は当業者に周知であり
、それらのそれぞれにより硬化を行うことができる。該
(メタ)アクリル酸エステル混合物は、それ自体単独で
、または他の単量体もしくは重合体と混合して使用する
事ができる。この新規な(メタ)アクリル酸エステル混
合物は、有機過酸化物の添加によっても重合させること
ができる。The reaction temperature may be in the range of 60 to 150°C, but from the viewpoint of shortening the reaction time and preventing polymerization, it is advantageous to carry out the reaction at a temperature of 75 to 120°C. Usually, a polymerization inhibitor is already added to acrylic acid or methacrylic acid.
A polymerization inhibitor may be added again during the reaction. Examples of such polymerization inhibitors include hydroquinone, P-methoxyphenol, 2,4-dimethyl-6-tert-butylphenol, α-nitroso-β-naphthol, P -benzoquinone, 2,5-dihydroxy-P-quinone, phenothiazine, N-nitrosodiphenylamine, copper salts and the like. The amount used is usually 0.0 to the reaction mixture.
It is 1 to 1% by weight. The (meth)acrylic acid ester mixture of the present invention thus obtained can be used for industrial purposes by washing with water or aqueous alkaline solution, etc., or separating it from the solvent by a method such as residual pressure distillation, if necessary. used for. The (meth)acrylic ester mixtures are useful as paints, hard coats, ink compositions and electronic materials, which can be cured by radiation or by thermal means. Radiation curing can be carried out by particulate radiation, such as ionizing or electron beams, or by actinic radiation, such as ultraviolet radiation. When curing is carried out by actinic radiation, the photopolymerization initiator includes many types of photoinitiators known in the art. Radiation curing techniques and heat curing techniques are well known to those skilled in the art, and curing can be accomplished by each of them. The (meth)acrylic acid ester mixture can be used alone or in combination with other monomers or polymers. This novel (meth)acrylic ester mixture can also be polymerized by addition of organic peroxides.
(実施例) 以下実施例を以て説明する。(Example) This will be explained below using examples.
実施例1
トリペンタエリスリトール356g ε−カプロラ
クトン1026g及び塩化第−スズ0.3gを仕込み、
反応温度170℃で反応液中のε−カプロラクトンが0
.1 重量%以下になるまで反応を継続しトリペンタエ
リスリトールとε−カプロラクトンの反応物を得た。こ
のものは、ワックス状の物質でOH価は242■KOH
/gである。Example 1 356 g of tripentaerythritol, 1026 g of ε-caprolactone and 0.3 g of stannous chloride were charged,
At a reaction temperature of 170°C, ε-caprolactone in the reaction solution was 0.
.. The reaction was continued until the concentration became 1% by weight or less to obtain a reaction product of tripentaerythritol and ε-caprolactone. This substance is a waxy substance with an OH value of 242 KOH.
/g.
上記で得たトリペンタエリスリトールとε−カプロラク
トンの反応物691g アクリル酸346g、P−1
−ルエンスルホン酸20g、ハイドロキノン3g、ベン
ゼン560g シクロヘキサン140gを仕込み、加
熱し、生成水は溶剤と共に蒸留、凝縮させ分離器で水の
み系外に取り除き、溶剤は、反応器に戻す。水が72g
生成した時点で冷却した。反応温度は84〜89℃であ
った0反応器合物をベンゼン1600g及びシクロヘキ
サン400gに溶解し、20z苛性ソダ水?8液で中和
した後、20χ食塩水400gで3回洗浄する。溶剤を
減圧留去して淡黄色の液体771gを得た。このものは
、下記の性質を有する。691 g of the reaction product of tripentaerythritol and ε-caprolactone obtained above 346 g of acrylic acid, P-1
- 20 g of luenesulfonic acid, 3 g of hydroquinone, and 560 g of benzene are charged and heated. The produced water is distilled and condensed together with the solvent, and only the water is removed from the system using a separator. The solvent is returned to the reactor. 72g of water
Once formed, it was cooled. The reaction temperature was 84-89°C.The reactor mixture was dissolved in 1600g of benzene and 400g of cyclohexane, and 20% caustic soda water was added. After neutralizing with 8 liquid, wash 3 times with 400 g of 20x saline solution. The solvent was distilled off under reduced pressure to obtain 771 g of a pale yellow liquid. This material has the following properties.
粘 度 (25℃) 210o cps屈折率
(25℃) 1.4825
得られた生成物の核磁気共鳴(NM)l)の測定を行っ
た結果を下記に示す。Viscosity (25°C) 210° cps Refractive index (25°C) 1.4825 The results of nuclear magnetic resonance (NM) measurement of the obtained product are shown below.
No、 吸収周波数(llz)1
2607.421
2 2597.656
3 2556.640
4 2498.046
5 2488.281
6 1974.609
1960.937
1931゜640
1921.875
1191.406
1158.203
1126.953
1052.734
964.843
943.359
660.156
646.484
507.812
425.781
382.812
367.187
o、oo。No, absorption frequency (llz) 1
2607.421 2 2597.656 3 2556.640 4 2498.046 5 2488.281 6 1974.609 1960.937 1931°640 1921.875 1191.406 1158.203 1126.953 1 052.734 964.843 943.359 660.156 646.484 507.812 425.781 382.812 367.187 o, oo.
なお、上記測定は、基準物質としてテトラメチルシラン
を用い溶媒は、重クロロホルムを用いて、プロトンデカ
ップリング法で行った。The above measurements were carried out by a proton decoupling method using tetramethylsilane as a reference substance and deuterated chloroform as a solvent.
実施例2
トリペンタエリスリトール及びテトラペンタエリスリト
ールの混合物(トリペンタエリスリトル57.3χ、テ
トラペンタエリスリトール25.6 %で、水酸基含有
量は33重景%) 200g、ε−カプロラクトン29
2.5g 、塩化第−スズ0.15gを仕込み、反応温
度170℃で反応液中のε−カプロラクトンが0.1
重量%以下になるまで反応を継続し、トリペンタエリス
リトール及びテトラペンタエリスリトールの混合物とε
−カプロラクトンの反応物を得た。このものは、ワック
ス状の物質で011価は415■KOH/gである。上
記で得たトリペンタエリスリトール及びテトラペンタエ
リスリトールの混合物とε−カプロラクトンの反応物4
03g アクリル酸 259g5P−1−ルエンスル
ホン酸15g 、ハイドロキノン2g1ヘンゼン400
g、シクロヘキサン500gを仕込み、加熱し、生成水
が54gになった時点で冷却した0反応器合物をベンゼ
ン1200g及びシクロヘキサン300gに溶解し、2
oχ苛性ソーダ水溶液で中和した後、20χ食塩水40
0gで3回洗浄する。溶剤を減圧留去して淡黄色の液体
485gを得た。Example 2 Mixture of tripentaerythritol and tetrapentaerythritol (tripentaerythritol 57.3χ, tetrapentaerythritol 25.6%, hydroxyl group content 33%) 200 g, ε-caprolactone 29
2.5 g of stannous chloride and 0.15 g of stannous chloride were charged, and at a reaction temperature of 170°C, ε-caprolactone in the reaction solution was reduced to 0.1
The reaction was continued until the concentration of tripentaerythritol and tetrapentaerythritol was reduced to ε
- A reaction product of caprolactone was obtained. This material is a wax-like substance and has a 011 value of 415 ■KOH/g. Reaction product 4 of the mixture of tripentaerythritol and tetrapentaerythritol obtained above and ε-caprolactone
03g acrylic acid 259g5P-1-luenesulfonic acid 15g, hydroquinone 2g1Hensen 400
g, 500 g of cyclohexane was charged, heated, and cooled when the produced water reached 54 g. The reactor mixture was dissolved in 1200 g of benzene and 300 g of cyclohexane, and 2
After neutralizing with ox caustic soda aqueous solution, 20x saline solution 40
Wash 3 times at 0g. The solvent was distilled off under reduced pressure to obtain 485 g of a pale yellow liquid.
このものは、下記の性質を有する。This material has the following properties.
粘 度 (25℃) 3400 CP
S屈折率 (25℃) 1.4831
得られた生成物の核磁気共鳴(NMR)の測定を行った
結果を下記に示す。Viscosity (25℃) 3400 CP
S refractive index (25° C.) 1.4831 The results of nuclear magnetic resonance (NMR) measurement of the obtained product are shown below.
No、 吸収周波数(It z )1
2607.421
2 2597.656
3 2498.046
4 2486.328
5 1974.609
6 1960.937
7 1931.640
8 1921.875
9 1191.406
IQ 1158.20311
1126.953
12 1052.734
13 964.84314
943.35915
660.15616
646.48417
507.81218
425.78119
382.81220
367.18721
0.000実施例3
トリペンタエリスリトール及びテトラペンタエリスリト
ールの混合物(トリペンタエリスリトル57.3χ、テ
トラペンタエリスリトール25.6χで、水酸基含有量
は、33重量%) 200g、ε−カプロラクトン44
3g、塩化第−スズ0.22gを仕込み、反応温度17
0℃で反応液中のε−カプロラクトンが0.1 重量%
以下になるまで反応を継続しトリペンタエリスリトール
及びテトラペンクエリスリトールの混合物とε−カプロ
ラクトンの反応物を得た。No, absorption frequency (It z ) 1
2607.421 2 2597.656 3 2498.046 4 2486.328 5 1974.609 6 1960.937 7 1931.640 8 1921.875 9 1191.406 IQ 1158.20311
1126.953 12 1052.734 13 964.84314
943.35915
660.15616
646.48417
507.81218
425.78119
382.81220
367.18721
0.000 Example 3 Mixture of tripentaerythritol and tetrapentaerythritol (tripentaerythritol 57.3χ, tetrapentaerythritol 25.6χ, hydroxyl group content 33% by weight) 200g, ε-caprolactone 44
3g and 0.22g of stannous chloride were charged, and the reaction temperature was 17.
ε-caprolactone in the reaction solution at 0°C is 0.1% by weight
The reaction was continued until the following reaction was achieved, and a reaction product of a mixture of tripentaerythritol and tetrapene erythritol and ε-caprolactone was obtained.
このものは、ワックス状の物質でOH価は320mgK
OH/gである。上記で得た反応物350g、メタクリ
ル酸207g、 P−トルエンスルホン酸12g、ハイ
ドロキが36gになった時点で冷却した。反応混合物を
トルエン1500gに熔解し、20χ苛性ソーダ水溶液
で中和した後20χ食塩水400gで3回洗浄する。?
8剤を減圧留去して淡黄色のl1体403gを得た。こ
のものは、下記の性質を有する。This substance is a waxy substance with an OH value of 320mgK.
OH/g. When the amount of the reactant obtained above was 350 g, 207 g of methacrylic acid, 12 g of P-toluenesulfonic acid, and 36 g of hydroxide, it was cooled. The reaction mixture was dissolved in 1500 g of toluene, neutralized with a 20x aqueous sodium hydroxide solution, and washed three times with 400 g of a 20x saline solution. ?
Agent 8 was distilled off under reduced pressure to obtain 403 g of pale yellow 11 compound. This material has the following properties.
粘 度 (25℃) 2090 CP
S屈折率 (25℃) 1.4827
得られた生成物の核磁気共鳴(NMR)の測定を行った
結果を下記に示す。Viscosity (25℃) 2090 CP
S refractive index (25° C.) 1.4827 The results of nuclear magnetic resonance (NMR) measurement of the obtained product are shown below.
No、 吸収周波数(It z )1
2607.421
2 2597.656
3 2515.625
4 2503.906
5 2050.781
6 2042.968
7 1892.578
8 1880.8599
1191.40610
1158.20311
1126.95312
1054.68713
966.79614
962.89015
945.31216
662.10917
646.48418 50
7.81219 425.
78120 382.8
1221 367、.18
722 273.4372
3 0.000応用例
1〜3
実施例1〜3で得た化合物、光重合開始剤を表−1の様
に配合し、紫外線で硬化し、鉛筆硬度、可トウ性、硬化
性を測定した。No, absorption frequency (It z ) 1
2607.421 2 2597.656 3 2515.625 4 2503.906 5 2050.781 6 2042.968 7 1892.578 8 1880.8599
1191.40610
1158.20311
1126.95312
1054.68713
966.79614
962.89015
945.31216
662.10917
646.48418 50
7.81219 425.
78120 382.8
1221 367,. 18
722 273.4372
3 0.000 Application Examples 1 to 3 The compounds obtained in Examples 1 to 3 and photopolymerization initiators were blended as shown in Table 1, cured with ultraviolet light, and measured for pencil hardness, towability, and curability. .
硬化性:紫外線を照射し、指触乾燥するまで秒数で表わ
す。Curability: Expressed in seconds until dry to the touch after irradiation with ultraviolet rays.
鉛筆硬度:硬質塩ビ板にロールコータ−で25μの厚さ
で塗布し、紫外線を照射し硬化さ
せたテストピースを、JISに5651−1966に準
じた測定による鉛筆硬度。Pencil hardness: Pencil hardness measured in accordance with JIS 5651-1966 using a test piece coated with a roll coater to a thickness of 25 μm on a hard PVC board and cured by irradiation with ultraviolet rays.
可トウ性:硬質塩ビシートにロールコータ−で25μの
厚さで塗布し、紫外線を照射し硬
化させ、硬化膜を180℃折りまげ、硬化膜の状態を観
察した。Towability: It was coated on a hard PVC sheet with a roll coater to a thickness of 25 μm, cured by irradiation with ultraviolet rays, and the cured film was bent at 180° C. and the condition of the cured film was observed.
◎−−・−−異常なし
○ −ややクラック発生
× 全面にクラック発生
表−1
(発明の効果)
本発明の(メタ)アクリル酸エステル混合物は、低粘度
で、硬化速度が速(、硬化物の硬度が硬く、可トウ性が
良好である。◎--・--No abnormality○ - Slight cracking × Cracking on the entire surface Table-1 (Effects of the invention) The (meth)acrylic acid ester mixture of the present invention has a low viscosity and a fast curing speed (, cured product It has high hardness and good towability.
特許出願人 日本化薬株式会社Patent applicant: Nippon Kayaku Co., Ltd.
Claims (1)
スリトールとε−カプロラクトンの反応物の(メタ)ア
クリル酸エステル混合物。A (meth)acrylic acid ester mixture of a reaction product of tripentaerythritol and/or tetrapentaerythritol and ε-caprolactone.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP19724888A JPH0248551A (en) | 1988-08-09 | 1988-08-09 | (meth)acrylic ester mixture |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP19724888A JPH0248551A (en) | 1988-08-09 | 1988-08-09 | (meth)acrylic ester mixture |
Publications (1)
Publication Number | Publication Date |
---|---|
JPH0248551A true JPH0248551A (en) | 1990-02-19 |
Family
ID=16371310
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
JP19724888A Pending JPH0248551A (en) | 1988-08-09 | 1988-08-09 | (meth)acrylic ester mixture |
Country Status (1)
Country | Link |
---|---|
JP (1) | JPH0248551A (en) |
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US5452548A (en) * | 1993-07-01 | 1995-09-26 | Kwon; Heug J. | Bearing structure with isolation and anchor device |
JPH08245901A (en) * | 1995-01-26 | 1996-09-24 | Daimler Benz Ag | Pigment with color relating to visual angle, its production and its use for coating material |
-
1988
- 1988-08-09 JP JP19724888A patent/JPH0248551A/en active Pending
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US5452548A (en) * | 1993-07-01 | 1995-09-26 | Kwon; Heug J. | Bearing structure with isolation and anchor device |
JPH08245901A (en) * | 1995-01-26 | 1996-09-24 | Daimler Benz Ag | Pigment with color relating to visual angle, its production and its use for coating material |
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