JP2020152646A - Component of hydrophilizing agent for plastic and hydrophilizing agent for plastic - Google Patents
Component of hydrophilizing agent for plastic and hydrophilizing agent for plastic Download PDFInfo
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- 239000003795 chemical substances by application Substances 0.000 title claims abstract description 25
- 239000004033 plastic Substances 0.000 title abstract description 17
- 229920003023 plastic Polymers 0.000 title abstract description 17
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 claims abstract description 24
- KWIUHFFTVRNATP-UHFFFAOYSA-O N,N,N-trimethylglycinium Chemical group C[N+](C)(C)CC(O)=O KWIUHFFTVRNATP-UHFFFAOYSA-O 0.000 claims abstract description 19
- SDXAWLJRERMRKF-UHFFFAOYSA-N 3,5-dimethyl-1h-pyrazole Chemical group CC=1C=C(C)NN=1 SDXAWLJRERMRKF-UHFFFAOYSA-N 0.000 claims abstract description 7
- 125000003545 alkoxy group Chemical group 0.000 claims abstract description 5
- 125000004432 carbon atom Chemical group C* 0.000 claims abstract description 5
- 125000005843 halogen group Chemical group 0.000 claims abstract description 5
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims abstract description 5
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims abstract description 5
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims abstract description 4
- 150000003377 silicon compounds Chemical class 0.000 claims description 33
- 150000001875 compounds Chemical class 0.000 claims description 23
- 238000006243 chemical reaction Methods 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims description 2
- 239000000758 substrate Substances 0.000 abstract description 12
- 239000002210 silicon-based material Substances 0.000 abstract description 7
- KWIUHFFTVRNATP-UHFFFAOYSA-N Betaine Natural products C[N+](C)(C)CC([O-])=O KWIUHFFTVRNATP-UHFFFAOYSA-N 0.000 abstract description 5
- 229960003237 betaine Drugs 0.000 abstract description 5
- WHIVNJATOVLWBW-UHFFFAOYSA-N n-butan-2-ylidenehydroxylamine Chemical group CCC(C)=NO WHIVNJATOVLWBW-UHFFFAOYSA-N 0.000 abstract 1
- -1 2-[(3,5-dimethylpyrazolyl) carbonylamino] ethyl Chemical group 0.000 description 12
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 8
- 239000002904 solvent Substances 0.000 description 8
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- 239000004417 polycarbonate Substances 0.000 description 5
- 229920000515 polycarbonate Polymers 0.000 description 5
- 239000007788 liquid Substances 0.000 description 4
- 239000002994 raw material Substances 0.000 description 4
- 125000000542 sulfonic acid group Chemical group 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- 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 3
- UUEWCQRISZBELL-UHFFFAOYSA-N 3-trimethoxysilylpropane-1-thiol Chemical compound CO[Si](OC)(OC)CCCS UUEWCQRISZBELL-UHFFFAOYSA-N 0.000 description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 235000019441 ethanol Nutrition 0.000 description 3
- 238000011156 evaluation Methods 0.000 description 3
- 239000012948 isocyanate Substances 0.000 description 3
- 238000000034 method Methods 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 2
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 2
- WTKZEGDFNFYCGP-UHFFFAOYSA-N Pyrazole Chemical compound C=1C=NNC=1 WTKZEGDFNFYCGP-UHFFFAOYSA-N 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- 239000002216 antistatic agent Substances 0.000 description 2
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 2
- 235000019400 benzoyl peroxide Nutrition 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000003759 ester based solvent Substances 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 229910044991 metal oxide Inorganic materials 0.000 description 2
- 150000004706 metal oxides Chemical class 0.000 description 2
- QYZFTMMPKCOTAN-UHFFFAOYSA-N n-[2-(2-hydroxyethylamino)ethyl]-2-[[1-[2-(2-hydroxyethylamino)ethylamino]-2-methyl-1-oxopropan-2-yl]diazenyl]-2-methylpropanamide Chemical compound OCCNCCNC(=O)C(C)(C)N=NC(C)(C)C(=O)NCCNCCO QYZFTMMPKCOTAN-UHFFFAOYSA-N 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 238000010992 reflux Methods 0.000 description 2
- 239000011347 resin Substances 0.000 description 2
- 229920005989 resin Polymers 0.000 description 2
- 239000008279 sol Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- LZDKZFUFMNSQCJ-UHFFFAOYSA-N 1,2-diethoxyethane Chemical compound CCOCCOCC LZDKZFUFMNSQCJ-UHFFFAOYSA-N 0.000 description 1
- XMNIXWIUMCBBBL-UHFFFAOYSA-N 2-(2-phenylpropan-2-ylperoxy)propan-2-ylbenzene Chemical compound C=1C=CC=CC=1C(C)(C)OOC(C)(C)C1=CC=CC=C1 XMNIXWIUMCBBBL-UHFFFAOYSA-N 0.000 description 1
- PFHOSZAOXCYAGJ-UHFFFAOYSA-N 2-[(2-cyano-4-methoxy-4-methylpentan-2-yl)diazenyl]-4-methoxy-2,4-dimethylpentanenitrile Chemical compound COC(C)(C)CC(C)(C#N)N=NC(C)(C#N)CC(C)(C)OC PFHOSZAOXCYAGJ-UHFFFAOYSA-N 0.000 description 1
- WYGWHHGCAGTUCH-UHFFFAOYSA-N 2-[(2-cyano-4-methylpentan-2-yl)diazenyl]-2,4-dimethylpentanenitrile Chemical compound CC(C)CC(C)(C#N)N=NC(C)(C#N)CC(C)C WYGWHHGCAGTUCH-UHFFFAOYSA-N 0.000 description 1
- KRDXTHSSNCTAGY-UHFFFAOYSA-N 2-cyclohexylpyrrolidine Chemical compound C1CCNC1C1CCCCC1 KRDXTHSSNCTAGY-UHFFFAOYSA-N 0.000 description 1
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical group [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 1
- DKPFZGUDAPQIHT-UHFFFAOYSA-N Butyl acetate Natural products CCCCOC(C)=O DKPFZGUDAPQIHT-UHFFFAOYSA-N 0.000 description 1
- 229930194542 Keto Natural products 0.000 description 1
- YIVJZNGAASQVEM-UHFFFAOYSA-N Lauroyl peroxide Chemical compound CCCCCCCCCCCC(=O)OOC(=O)CCCCCCCCCCC YIVJZNGAASQVEM-UHFFFAOYSA-N 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- KYIKRXIYLAGAKQ-UHFFFAOYSA-N abcn Chemical compound C1CCCCC1(C#N)N=NC1(C#N)CCCCC1 KYIKRXIYLAGAKQ-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 238000007259 addition reaction Methods 0.000 description 1
- 239000005456 alcohol based solvent Substances 0.000 description 1
- 150000001338 aliphatic hydrocarbons Chemical class 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000008280 blood Substances 0.000 description 1
- 210000004369 blood Anatomy 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 125000001309 chloro group Chemical group Cl* 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- LSXWFXONGKSEMY-UHFFFAOYSA-N di-tert-butyl peroxide Chemical compound CC(C)(C)OOC(C)(C)C LSXWFXONGKSEMY-UHFFFAOYSA-N 0.000 description 1
- 238000007865 diluting Methods 0.000 description 1
- 125000001301 ethoxy group Chemical group [H]C([H])([H])C([H])([H])O* 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- FUZZWVXGSFPDMH-UHFFFAOYSA-N hexanoic acid Chemical compound CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 description 1
- LRDFRRGEGBBSRN-UHFFFAOYSA-N isobutyronitrile Chemical compound CC(C)C#N LRDFRRGEGBBSRN-UHFFFAOYSA-N 0.000 description 1
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 125000005641 methacryl group Chemical group 0.000 description 1
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- QIOYHIUHPGORLS-UHFFFAOYSA-N n,n-dimethyl-3-trimethoxysilylpropan-1-amine Chemical compound CO[Si](OC)(OC)CCCN(C)C QIOYHIUHPGORLS-UHFFFAOYSA-N 0.000 description 1
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 102000004169 proteins and genes Human genes 0.000 description 1
- 108090000623 proteins and genes Proteins 0.000 description 1
- 125000003226 pyrazolyl group Chemical group 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- FDRCDNZGSXJAFP-UHFFFAOYSA-M sodium chloroacetate Chemical compound [Na+].[O-]C(=O)CCl FDRCDNZGSXJAFP-UHFFFAOYSA-M 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 125000004213 tert-butoxy group Chemical group [H]C([H])([H])C(O*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
Landscapes
- Coating Of Shaped Articles Made Of Macromolecular Substances (AREA)
- Paints Or Removers (AREA)
Abstract
Description
本発明は、親水効果や防曇効果が大きく、省エネルギーで製造できるコーティング可能な親水化剤あるいは防曇剤の成分として有用なケイ素系化合物に関する。 The present invention relates to a silicon-based compound which has a large hydrophilic effect and anti-fog effect and is useful as a component of a coatable hydrophilic agent or anti-fog agent which can be produced with energy saving.
本発明者らは、親水化剤の材料に関する数多くの特許出願を行っている。
その中で、今回の発明に関係する代表的な特許出願を以下に示す。
プラスチック基板(例えばポリカーボネート)の表面親水化剤として、本発明者らは既にスルホン酸基及びブロックドイソシアネート基を持つケイ素化合物で修飾した金属酸化物ゾルを特許出願している(特許文献1実施例6)。またベタイン基及びブロックドイソシアネート基を持つケイ素化合物の加水分解縮合物からなる親水化剤も特許出願している(特許文献2実施例1−5、1−9)。特許文献1に記載の親水性基がスルホン酸基を有するケイ素化合物で修飾された金属酸化物ゾルの場合は、プラスチックに対して耐久性の高い親水性を示す。これはブロックドイソシアネート基が加熱によりイソシアネート基が生成してプラスチック基板上に存在する水酸基と化学反応して強固に結合することに起因する。しかし、特許文献2に記載の親水性基がベタイン基を有するケイ素化合物の加水分解縮合物の場合は、耐久性が劣るという問題がある。これは、先行技術に記載されている3−イソシアネートプロピルトリエトキシシランと3,5−ジメチルピラゾールとの反応生成物であるブロックドイソシアネート基を有するケイ素化合物の分子鎖長が、スルホン酸基を有するケイ素化合物の分子鎖長よりは長いが、ベタイン基を有するケイ素化合物の分子鎖長よりは短いためと考えられる。
すなわち親水性基がスルホン酸基の場合は、ブロックドイソシアネート基は基板のプラスチック表面に接することが出来るので所定の温度以上ではプラスチック基板と反応が可能で、耐久性の高い親水性を発現できる。しかし、親水性基がベタイン基の場合で、ブロックドイソシアネート基を有するケイ素化合物の分子鎖長がベタイン基を有するケイ素化合物の分子鎖長よりは短い場合は、ブロックドイソシアネート基が基板のプラスチック表面に接することが困難なために基板と反応しづらく、耐久性の高い親水性を発現できないと考えられる。
The present inventors have filed numerous patent applications regarding the material of the hydrophilizing agent.
Among them, typical patent applications related to this invention are shown below.
As a surface hydrophilic agent for a plastic substrate (for example, polycarbonate), the present inventors have already applied for a patent application for a metal oxide sol modified with a silicon compound having a sulfonic acid group and a blocked isocyanate group (Patent Document 1 Example). 6). A patent application has also been filed for a hydrophilizing agent composed of a hydrolyzed condensate of a silicon compound having a betaine group and a blocked isocyanate group (Patent Document 2, Examples 1-5 and 1-9). In the case of a metal oxide sol in which the hydrophilic group described in Patent Document 1 is modified with a silicon compound having a sulfonic acid group, it exhibits highly durable hydrophilicity with respect to plastics. This is because the blocked isocyanate group is heated to generate an isocyanate group and chemically reacts with the hydroxyl group existing on the plastic substrate to form a strong bond. However, in the case of a hydrolyzed condensate of a silicon compound in which the hydrophilic group described in Patent Document 2 has a betaine group, there is a problem that the durability is inferior. This is because the molecular chain length of a silicon compound having a blocked isocyanate group, which is a reaction product of 3-isocyanatepropyltriethoxysilane and 3,5-dimethylpyrazole described in the prior art, has a sulfonic acid group. It is considered that this is because it is longer than the molecular chain length of the silicon compound, but shorter than the molecular chain length of the silicon compound having a betaine group.
That is, when the hydrophilic group is a sulfonic acid group, the blocked isocyanate group can come into contact with the plastic surface of the substrate, so that it can react with the plastic substrate at a predetermined temperature or higher, and can exhibit highly durable hydrophilicity. However, when the hydrophilic group is a betaine group and the molecular chain length of the silicon compound having a blocked isocyanate group is shorter than the molecular chain length of the silicon compound having a betaine group, the blocked isocyanate group is on the plastic surface of the substrate. It is considered that it is difficult to react with the substrate because it is difficult to come into contact with the substrate, and it is not possible to develop highly durable hydrophilicity.
本発明の目的は、プラスチック基板に対して耐久性の高い親水性を示すベタイン系親水化剤を提供するために必要な、ベタイン基を有するケイ素化合物より長い分子鎖を有するブロックイソシアネート基を有するケイ素系化合物を提供することである。 An object of the present invention is silicon having a blocked isocyanate group having a molecular chain longer than that of a silicon compound having a betaine group, which is necessary for providing a betaine-based hydrophilic agent having high hydrophilicity to a plastic substrate. It is to provide a system compound.
本発明者らは、鋭意研究を重ねた結果、耐久性の高いベタイン系親水化剤を得るために必要なブロックイソシアネート基含有ケイ素化合物を見出し、下記に示す発明を完成させた。
本発明のケイ素系化合物は、
〔1〕 下記式(1)
(X1)3−o−Si(CH3)o−(CH2)p−S−CH2CHYCOO(CH2)q(OCH2CH2)rNHCO−Z (1)
{式中X1は炭素数1〜6のアルコキシ基、ハロゲン原子及び水酸基であり、oは0又は1であり、pは1〜5の整数であり、Yはメチル基又は水素原子であり、qは1〜4の整数であり、rは0又は1であり、Zは3,5−ジメチルピラゾール基又はメチルエチルケトオキシム基である}で表されるブロックイソシアネート基含有ケイ素系化合物。
〔2〕 下記式(2)で表される化合物と
(X1)3−o−Si(CH3)o−(CH2)p−SH (2)
{式中X1、o 及びpは前記一般式(1)と同一である}
下記式(3)で表される化合物
CH2=CYCOO(CH2)q(OCH2CH2)rNHCO−Z (3)
{式中Y、q、r及びZは前記一般式(1)と同一である}
を反応させることを特徴とする前記一般式(1)で表されるブロックイソシアネート基含有ケイ素化合物の製造方法。
〔3〕 少なくとも前記一般式(1)で表されるブロックイソシアネート基含有ケイ素化合物及びベタイン基含有ケイ素系化合物を含むことを特徴とする親水化剤。
As a result of diligent research, the present inventors have found a blocked isocyanate group-containing silicon compound necessary for obtaining a highly durable betaine-based hydrophilic agent, and have completed the invention shown below.
The silicon compound of the present invention is
[1] The following formula (1)
(X 1) 3-o -Si (CH 3) o - (CH 2) p -S-CH 2 CHYCOO (CH 2) q (OCH 2 CH 2) r NHCO-Z (1)
{In the formula, X 1 is an alkoxy group having 1 to 6 carbon atoms, a halogen atom and a hydroxyl group, o is 0 or 1, p is an integer of 1 to 5, and Y is a methyl group or a hydrogen atom. q is an integer of 1 to 4, r is 0 or 1, and Z is a 3,5-dimethylpyrazole group or a methylethylketooxime group}, which is a blocked isocyanate group-containing silicon-based compound.
[2] Compounds represented by the following formula (2) and (X 1 ) 3-o- Si (CH 3 ) o- (CH 2 ) p- SH (2)
{X 1, o and p in the formula is the same as the general formula (1)}
Compound CH 2 represented by the following formula (3) = CYCOO (CH 2 ) q (OCH 2 CH 2 ) r NHCO-Z (3)
{Y, q, r and Z in the formula are the same as the general formula (1)}
A method for producing a blocked isocyanate group-containing silicon compound represented by the general formula (1), which comprises reacting.
[3] A hydrophilic agent containing at least a blocked isocyanate group-containing silicon compound represented by the general formula (1) and a betaine group-containing silicon compound.
本発明の、ベタイン基を有するケイ素化合物より長い分子鎖のブロックイソシアネート基を有するケイ素化合物を用いることにより、プラスチック基板にイソシアネート基が接して化学反応して化学結合することにより、親水性基がベタイン基であってもプラスチック基板に対して耐久性の高い親水化剤を提供することが出来る。 By using the silicon compound having a blocked isocyanate group having a longer molecular chain than the silicon compound having a betaine group of the present invention, the isocyanate group comes into contact with the plastic substrate and chemically reacts to form a chemical bond, whereby the hydrophilic group becomes betaine. It is possible to provide a hydrophilic agent having high durability against a plastic substrate even if it is a group.
本発明の前記一般式(1)で表される化合物について説明する。 The compound represented by the general formula (1) of the present invention will be described.
本発明の化合物である一般式(1)で表される化合物は、X1の炭素数1〜6のアルコキシ基としては、メトキシ基、エトキシ基、イソプロピル基、n−プロピル基、tert−ブトキシ基、n−ブトキシ基等が挙げられる。これらのうち好ましくは、メチル基及びエチル基である。
また、X1のハロゲン原子としては、塩素原子または臭素原子である。
Compound represented by the general formula is a compound of the present invention (1), as the alkoxy group having 1 to 6 carbon atoms of X 1, a methoxy group, an ethoxy group, an isopropyl group, n- propyl group, tert- butoxy group , N-butoxy group and the like. Of these, a methyl group and an ethyl group are preferable.
The halogen atom of X 1 is a chlorine atom or a bromine atom.
oは0または1であり、好ましくは0である。
pは1〜5の整数であり、好ましくは2〜4であり、最も好ましくは3である。
qは1〜4の整数であり、好ましくは2〜3であり、最も好ましくは2である。
o is 0 or 1, preferably 0.
p is an integer of 1-5, preferably 2-4, and most preferably 3.
q is an integer of 1 to 4, preferably 2 to 3, and most preferably 2.
前記一般式(1)で表される具体的な化合物としては以下の化合物が挙げられる。
ただし−Z1は3,5−ジメチルピラゾール基を表す。
(CH3O)3SiCH2CH2CH2SCH2CH(CH3)COOCH2CH2NHCO−Z1 (1)
(CH3O)2(CH3)SiCH2CH2CH2SCH2CH(CH3)COOCH2CH2NHCO−Z1 (2)
(C2H5O)3SiCH2CH2CH2SCH2CH(CH3)COOCH2CH2NHCO−Z1 (3)
(CH3O)3SiCH2CH2CH2SCH2CH2COOCH2CH2NHCO−Z1 (4)
(CH3O)2(CH3)SiCH2CH2CH2SCH2CH2COOCH2CH2NHCO−Z1 (5)
(C2H5O)3SiCH2CH2CH2SCH2CH2COOCH2CH2NHCO−Z1 (6)
(CH3O)3SiCH2CH2CH2SCH2CH(CH3)COOCH2CH2OCH2CH2NHCO−Z1 (7)
(CH3O)2(CH3)SiCH2CH2CH2SCH2CH(CH3)COOCH2CH2OCH2CH2NHCO−Z1 (8)
(C2H5O)3SiCH2CH2CH2SCH2CH(CH3)COOCH2CH2OCH2CH2NHCO−Z1 (9)
(CH3O)3SiCH2CH2CH2SCH2CH2COOCH2CH2OCH2CH2NHCO−Z1 (10)
(CH3O)2(CH3)SiCH2CH2CH2SCH2CH2COOCH2CH2OCH2CH2NHCO−Z1 (11)
(C2H5O)3SiCH2CH2CH2SCH2CH2COOCH2CH2 OCH2CH2NHCO−Z1 (12)
(CH3O)3SiCH2CH2CH2SCH2CH(CH3)COOCH2CH2NHCO−ON=C(CH3)(C2H5) (13)
(CH3O)2(CH3)SiCH2CH2CH2SCH2CH(CH3)COOCH2CH2NHCO−ON=C(CH3)(C2H5) (14)
(C2H5O)3SiCH2CH2CH2SCH2CH(CH3)COOCH2CH2NHCO−ON=C(CH3)(C2H5) (15)
(CH3O)3SiCH2CH2CH2SCH2CH2COOCH2CH2NHCO−ON=C(CH3)(C2H5) (16)
(CH3O)2(CH3)SiCH2CH2CH2SCH2CH2COOCH2CH2NHCO−ON=C(CH3)(C2H5) (17)
(C2H5O)3SiCH2CH2CH2SCH2CH2COOCH2CH2NHCO−ON=C(CH3)(C2H5) (18)
(CH3O)3SiCH2CH2CH2SCH2CH(CH3)COOCH2CH2OCH2CH2NHCO−ON=C(CH3)(C2H5) (19)
(CH3O)2(CH3)SiCH2CH2CH2SCH2CH(CH3)COOCH2CH2OCH2CH2NHCO−ON=C(CH3)(C2H5) (20)
(C2H5O)3SiCH2CH2CH2SCH2CH(CH3)COOCH2CH2OCH2CH2NHCO−ON=C(CH3)(C2H5) (21)
(CH3O)3SiCH2CH2CH2SCH2CH2COOCH2CH2OCH2CH2NHCO−ON=C(CH3)(C2H5) (22)
(CH3O)2(CH3)SiCH2CH2CH2SCH2CH2COOCH2CH2OCH2CH2NHCO−ON=C(CH3)(C2H5) (23)
(C2H5O)3SiCH2CH2CH2SCH2CH2COOCH2CH2OCH2CH2NHCO−ON=C(CH3)(C2H5) (24)
(CH3O)3SiCH2CH2CH2NHCH2CH(CH3)COOCH2CH2NHCO−ON=C(CH3)(C2H5) (25)
Specific examples of the compound represented by the general formula (1) include the following compounds.
Where -Z 1 represents a 3,5-dimethylpyrazole group.
(CH 3 O) 3 SiCH 2 CH 2 CH 2 SCH 2 CH (CH 3 ) COOCH 2 CH 2 NHCO-Z 1 (1)
(CH 3 O) 2 (CH 3) SiCH 2 CH 2 CH 2 SCH 2 CH (CH 3) COOCH 2 CH 2 NHCO-Z 1 (2)
(C 2 H 5 O) 3 SiCH 2 CH 2 CH 2 SCH 2 CH (CH 3 ) COOCH 2 CH 2 NHCO-Z 1 (3)
(CH 3 O) 3 SiCH 2 CH 2 CH 2 SCH 2 CH 2 COOCH 2 CH 2 NHCO-Z 1 (4)
(CH 3 O) 2 (CH 3) SiCH 2 CH 2 CH 2 SCH 2 CH 2 COOCH 2 CH 2 NHCO-Z 1 (5)
(C 2 H 5 O) 3 SiCH 2 CH 2 CH 2 SCH 2 CH 2 COOCH 2 CH 2 NHCO-Z 1 (6)
(CH 3 O) 3 SiCH 2 CH 2 CH 2 SCH 2 CH (CH 3 ) COOCH 2 CH 2 OCH 2 CH 2 NHCO-Z 1 (7)
(CH 3 O) 2 (CH 3) SiCH 2 CH 2 CH 2 SCH 2 CH (CH 3) COOCH 2 CH 2 OCH 2 CH 2 NHCO-Z 1 (8)
(C 2 H 5 O) 3 SCH 2 CH 2 CH 2 SCH 2 CH (CH 3 ) COOCH 2 CH 2 OCH 2 CH 2 NHCO-Z 1 (9)
(CH 3 O) 3 SiCH 2 CH 2 CH 2 SCH 2 CH 2 COOCH 2 CH 2 OCH 2 CH 2 NHCO-Z 1 (10)
(CH 3 O) 2 (CH 3) SiCH 2 CH 2 CH 2 SCH 2 CH 2 COOCH 2 CH 2 OCH 2 CH 2 NHCO-Z 1 (11)
(C 2 H 5 O) 3 SiCH 2 CH 2 CH 2 SCH 2 CH 2 COOCH 2 CH 2 OCH 2 CH 2 NHCO-Z 1 (12)
(CH 3 O) 3 SiCH 2 CH 2 CH 2 SCH 2 CH (CH 3 ) COOCH 2 CH 2 NHCO-ON = C (CH 3 ) (C 2 H 5 ) (13)
(CH 3 O) 2 (CH 3 ) SCH 2 CH 2 CH 2 SCH 2 CH (CH 3 ) COOCH 2 CH 2 NHCO-ON = C (CH 3 ) (C 2 H 5 ) (14)
(C 2 H 5 O) 3 SCH 2 CH 2 CH 2 SCH 2 CH (CH 3 ) COOCH 2 CH 2 NHCO-ON = C (CH 3 ) (C 2 H 5 ) (15)
(CH 3 O) 3 SiCH 2 CH 2 CH 2 SCH 2 CH 2 COOCH 2 CH 2 NHCO-ON = C (CH 3 ) (C 2 H 5 ) (16)
(CH 3 O) 2 (CH 3 ) SCH 2 CH 2 CH 2 SCH 2 CH 2 COOCH 2 CH 2 NHCO-ON = C (CH 3 ) (C 2 H 5 ) (17)
(C 2 H 5 O) 3 SiCH 2 CH 2 CH 2 SCH 2 CH 2 COOCH 2 CH 2 NHCO-ON = C (CH 3 ) (C 2 H 5 ) (18)
(CH 3 O) 3 SiCH 2 CH 2 CH 2 SCH 2 CH (CH 3 ) COOCH 2 CH 2 OCH 2 CH 2 NHCO-ON = C (CH 3 ) (C 2 H 5 ) (19)
(CH 3 O) 2 (CH 3 ) SCH 2 CH 2 CH 2 SCH 2 CH (CH 3 ) COOCH 2 CH 2 OCH 2 CH 2 NHCO-ON = C (CH 3 ) (C 2 H 5 ) (20)
(C 2 H 5 O) 3 SiCH 2 CH 2 CH 2 SCH 2 CH (CH 3 ) COOCH 2 CH 2 OCH 2 CH 2 NHCO-ON = C (CH 3 ) (C 2 H 5 ) (21)
(CH 3 O) 3 SiCH 2 CH 2 CH 2 SCH 2 CH 2 COOCH 2 CH 2 OCH 2 CH 2 NHCO-ON = C (CH 3 ) (C 2 H 5 ) (22)
(CH 3 O) 2 (CH 3 ) SCH 2 CH 2 CH 2 SCH 2 CH 2 COOCH 2 CH 2 OCH 2 CH 2 NHCO-ON = C (CH 3 ) (C 2 H 5 ) (23)
(C 2 H 5 O) 3 SiCH 2 CH 2 CH 2 SCH 2 CH 2 COOCH 2 CH 2 OCH 2 CH 2 NHCO-ON = C (CH 3 ) (C 2 H 5 ) (24)
(CH 3 O) 3 SiCH 2 CH 2 CH 2 NHCH 2 CH (CH 3 ) COOCH 2 CH 2 NHCO-ON = C (CH 3 ) (C 2 H 5 ) (25)
本発明の前記一般式(1)で表されるブロックイソシアネート基含有ケイ素化合物は以下の方法により得られる。
すなわち、前記一般式(2)で表されると前記一般式(3)で表される化合物を不活性雰囲気下、ラジカル発生剤の存在下加熱することにより得ることが出来る。
この際溶剤で希釈してもしなくても良い。
The blocked isocyanate group-containing silicon compound represented by the general formula (1) of the present invention can be obtained by the following method.
That is, the compound represented by the general formula (2) can be obtained by heating the compound represented by the general formula (3) in the presence of a radical generator in an inert atmosphere.
At this time, it may or may not be diluted with a solvent.
反応温度は、室温から120℃であり、好ましくは60〜100℃である。 The reaction temperature is from room temperature to 120 ° C, preferably 60 to 100 ° C.
反応時間は、2〜24時間あり、好ましくは6〜24時間である。 The reaction time is 2 to 24 hours, preferably 6 to 24 hours.
前記一般式(2)で表される化合物に対する、前記一般式(3)で表される化合物のモル比は0.95〜1.05であり、好ましくは1.0である。 The molar ratio of the compound represented by the general formula (3) to the compound represented by the general formula (2) is 0.95 to 1.05, preferably 1.0.
ラジカル発生剤としては、アゾ系化合物及び過酸化物系化合物が挙げられる。 Examples of the radical generator include azo compounds and peroxide compounds.
前記アゾ系化合物としては、2,2’−アゾビス(4−メトキシ−2,4−ジメチルバレロニトリル)、2,2’−アゾビス(2,4−ジメチルバレロニトリル)、2,2’−アゾビス(イソブチロニトリル)及び1,1’−アゾビス(シクロヘキサン−1−カルボニトリル)等が挙げられる。
これらのうち好ましいのは、2,2’−アゾビス(イソブチロニトリル)である。
Examples of the azo compound include 2,2'-azobis (4-methoxy-2,4-dimethylvaleronitrile), 2,2'-azobis (2,4-dimethylvaleronitrile), and 2,2'-azobis (2,2'-azobis). Isobutyronitrile) and 1,1'-azobis (cyclohexane-1-carbonitrile) and the like.
Of these, 2,2'-azobis (isobutyronitrile) is preferred.
前記過酸化物系化合物としては、ジラウロイルパーオキサイド、ジベンゾイルパーオキサイド、ジ−tert−ブチルパーオキサイド、ジクミルパーオキサイド及びtert−ブチルクミルパーオキサイド等が挙げられる。
これらのうち好ましいのは、ジベンゾイルパーオキサイドである。
Examples of the peroxide compound include dilauroyl peroxide, dibenzoyl peroxide, di-tert-butyl peroxide, dicumyl peroxide and tert-butyl cumyl peroxide.
Of these, dibenzoyl peroxide is preferred.
溶媒は用いても用いなくてもよい。溶媒を用いる場合、溶剤としては、芳香族炭化水素系溶剤(ベンゼン、トルエン及びキシレン等)、脂肪族炭化水素系溶剤(ヘプタン及びオクタン等)、エーテル系溶剤(テトラハイドロフラン、1,2−ジメトキシエタン及び1,2−ジエトキシエタン等)、アルコール系溶剤(メタノール、エタノール及びイソプロパノール等)、エステル系溶剤(酢酸エチル及び酢酸ブチル等)等が挙げられる。
これらのうち好ましいのは、芳香族系炭化水素及びエステル系溶剤であり、無溶媒がさらに好ましい。
The solvent may or may not be used. When a solvent is used, the solvent includes an aromatic hydrocarbon solvent (benzene, toluene, xylene, etc.), an aliphatic hydrocarbon solvent (heptane, octane, etc.), and an ether solvent (tetrahydrofuran, 1,2-dimethoxy). Etane and 1,2-diethoxyethane, etc.), alcohol solvents (methanol, ethanol, isopropanol, etc.), ester solvents (ethyl acetate, butyl acetate, etc.) and the like can be mentioned.
Of these, aromatic hydrocarbons and ester-based solvents are preferable, and solvent-free is even more preferable.
前記一般式(2)で表される具体的な化合物としては以下の物が挙げられる。
(CH3O)3SiCH2CH2CH2SH
(C2H5O)3SiCH2CH2CH2SH
(CH3O)2(CH3)SiCH2CH2CH2SH
これらの化合物は市販品として手に入れることが出来る。
Specific examples of the compound represented by the general formula (2) include the following compounds.
(CH 3 O) 3 SiCH 2 CH 2 CH 2 SH
(C 2 H 5 O) 3 SiCH 2 CH 2 CH 2 SH
(CH 3 O) 2 (CH 3 ) SiC H 2 CH 2 CH 2 SH
These compounds are available as commercial products.
前記一般式(3)で表される具体的な化合物としては以下の物が挙げられる。
ただし、Z1は3,5−ジメチルピラゾール基を表す。
CH2=C(CH3)COOCH2CH2NHCO−Z1
CH2=CHCOOCH2CH2NHCO−Z1
CH2=C(CH3)COOCH2CH2OCH2CH2NHCO−Z1
CH2=CHCOOCH2CH2OCH2CH2NHCO−Z1
CH2=C(CH3)COOCH2CH2NHCO−ON=C(CH3)(C2H5)
CH2=CHCOOCH2CH2NHCO−ON=C(CH3)(C2H5)
CH2=C(CH3)COOCH2CH2OCH2CH2NHCO−ON=C(CH3)(C2H5)
CH2=CHCOOCH2CH2OCH2CH2NHCOON=C(CH3)(C2H5)
Specific examples of the compound represented by the general formula (3) include the following compounds.
However, Z 1 represents a 3,5-dimethylpyrazole group.
CH 2 = C (CH 3 ) COOCH 2 CH 2 NHCO-Z 1
CH 2 = CHCOOCH 2 CH 2 NHCO-Z 1
CH 2 = C (CH 3 ) COOCH 2 CH 2 OCH 2 CH 2 NHCO-Z 1
CH 2 = CHCOOCH 2 CH 2 OCH 2 CH 2 NHCO-Z 1
CH 2 = C (CH 3 ) COOCH 2 CH 2 NHCO-ON = C (CH 3 ) (C 2 H 5 )
CH 2 = CHCOOCH 2 CH 2 NHCO-ON = C (CH 3 ) (C 2 H 5 )
CH 2 = C (CH 3 ) COOCH 2 CH 2 OCH 2 CH 2 NHCO-ON = C (CH 3 ) (C 2 H 5 )
CH 2 = CHCOOCH 2 CH 2 OCH 2 CH 2 NHCOON = C (CH 3 ) (C 2 H 5 )
これらの化合物は市販品として入手するか、あるいはピラゾール基又はメチルエチルケトオキシム基が付加していないイソシアネート化合物と固体のピラゾール又は液体のメチルケトオキシムを反応させることにより得ることが出来る。 These compounds can be obtained as commercial products, or can be obtained by reacting an isocyanate compound to which no pyrazole group or methyl ethyl ketooxime group is added with solid pyrazole or liquid methyl keto oxime.
すなわち、イソシアネート化合物とピラゾール又はメチルエチルケトオキシムを無溶媒で室温から100℃で等モル混合することにより付加反応が進行し、容易に得ることが出来る。 That is, the addition reaction proceeds and can be easily obtained by mixing the isocyanate compound with pyrazole or methyl ethyl ketooxime in an equimolar amount from room temperature to 100 ° C. without a solvent.
本発明のケイ素系化合物は、樹脂(例えばポリカーボネート)の親水(防曇)化剤の原料として有用である。
本ケイ素化合物を用いることにより、親水(防曇)性を発揮するベタイン基を有するケイ素化合物のよりも分子鎖が長いため、樹脂と接触しやすくなり、接着性が増して耐久性が向上すると考えられる。
The silicon-based compound of the present invention is useful as a raw material for a hydrophilic (anti-fog) agent for a resin (for example, polycarbonate).
It is thought that the use of this silicon compound has a longer molecular chain than the silicon compound having a betaine group that exhibits hydrophilicity (anti-fog), so that it becomes easier to contact with the resin, the adhesiveness increases, and the durability improves. Be done.
本発明のブロックイソシアネート基含有ケイ素化合物を用いる量としては、ベタイン基含有ケイ素化合物に対して、10〜100重量%であり、好ましくは20〜80重量%である。 The amount of the blocked isocyanate group-containing silicon compound of the present invention to be used is 10 to 100% by weight, preferably 20 to 80% by weight, based on the betaine group-containing silicon compound.
以下に実施例を示し、本発明を具体的に説明する。実施例は、本発明を説明するものであり、制限を加えるものではない。 Examples will be shown below, and the present invention will be specifically described. The examples illustrate the invention and do not impose any restrictions.
〔実施例1〕
ブロックドイソシアネート化合物、2−[(3,5−ジメチルピラゾリル)カルボニルアミノ]エチルメタクリレート(昭和電工株式会社製、商品名:カレンズMOI−BP)25.1g(100mmol)と3−メルカプトプロピルトリメトキシシラン(信越化学工業社製)19.6(100mmol)gを混合してアルゴンを20分間バブリングした。その中へアゾビスイソブチロニトリル164mg(1mmol)を加え、80℃で一晩加熱撹拌することにより本発明の化合物(1)を得た。H1−NMRより原料のメタクリル基プロトンの吸収(5.6ppm、5.91ppm及び6.15ppm)が消滅していることを確認した。
図1、2及び3に原料である2−[(3,5−ジメチルピラゾリル)カルボニルアミノ]エチルメタクリレート、3−メルカプトプロピルトリメトキシシラン及び本発明の化合物(1)のNMRチャートを示す。
[Example 1]
Blocked isocyanate compound, 2-[(3,5-dimethylpyrazolyl) carbonylamino] ethyl methacrylate (manufactured by Showa Denko Co., Ltd., trade name: Karenz MOI-BP) 25.1 g (100 mmol) and 3-mercaptopropyltrimethoxysilane (Manufactured by Shin-Etsu Chemical Co., Ltd.) 19.6 (100 mmol) g was mixed and argon was bubbled for 20 minutes. 164 mg (1 mmol) of azobisisobutyronitrile was added thereto, and the mixture was heated and stirred at 80 ° C. overnight to obtain the compound (1) of the present invention. H 1 absorption of the material of the methacryl group proton from -NMR (5.6ppm, 5.91ppm and 6.15 ppm) were confirmed to have disappeared.
FIGS. 1, 2 and 3 show NMR charts of 2-[(3,5-dimethylpyrazolyl) carbonylamino] ethyl methacrylate, 3-mercaptopropyltrimethoxysilane and the compound (1) of the present invention as raw materials.
〔使用例1〕
[3−(N,N−ジメチルアミノ)プロピル]トリメトキシシラン(東京化成工業株式会社製)5.2g(25mmol)、実施例1で得た本発明の化合物(1)3.0g(6.7mmol)、特開平2017−061439号公報の実施例1に記載の方法で得た界面活性剤2.0gをエチルアルコール10ml及び水5mlに溶解させ一晩加熱還流した。冷却後、クロロ酢酸ナトリウム(ナカライテスク社製)2.91g(25mmol)及び水5mlを加えさらに一晩加熱還流して水を加えることにより親水化剤(1)を得た。
[Usage example 1]
[3- (N, N-dimethylamino) propyl] Trimethoxysilane (manufactured by Tokyo Chemical Industry Co., Ltd.) 5.2 g (25 mmol), 3.0 g (6.) Of the compound of the present invention obtained in Example 1. 7 mmol), 2.0 g of the surfactant obtained by the method described in Example 1 of JP-A-2017-061439 was dissolved in 10 ml of ethyl alcohol and 5 ml of water, and the mixture was heated under reflux overnight. After cooling, 2.91 g (25 mmol) of sodium chloroacetate (manufactured by Nacalai Tesque, Inc.) and 5 ml of water were added, and the mixture was further heated under reflux overnight to add water to obtain a hydrophilic agent (1).
〔比較例1〕
使用例1において本発明の化合物(1)の代わりに、WOA12016167097号公報合成例4に記載の方法で得たケイ素系化合物3.0gを用いた以外は同様の操作を行うことにより親水化剤(2)を得た。
[Comparative Example 1]
In Example 1, instead of the compound (1) of the present invention, 3.0 g of the silicon-based compound obtained by the method described in Synthesis Example 4 of WOA12016167097 was used, and the same operation was carried out to make the hydrophilic agent (hydrophilicizing agent (). 2) was obtained.
耐久評価結果
使用例1及び比較例1で得た親水化剤をメタノールで25倍に希釈したコーティング液で以下の様に所定の基板の表面を改質し、初期の接触角及び水滴を垂らしてキムワイプで拭く操作を10回繰り返した後の接触角を測定し、その値から耐久性を評価した。
Durability evaluation results The surface of a predetermined substrate is modified as follows with a coating solution obtained by diluting the hydrophilic agent obtained in Use Example 1 and Comparative Example 1 with methanol 25 times, and the initial contact angle and water droplets are dropped. The contact angle after repeating the operation of wiping with a Kimwipe 10 times was measured, and the durability was evaluated from the value.
〔親水性評価サンプルの作製〕
ポリカーボネート板{76mm、26mm、1.0mm;エタノールで洗浄したもの}を処理液(表面親水化剤)に浸漬し、ポリカーボネート板を取り出した後、液切りをし、130℃、1間加熱処理した表面防曇ポリカーボネート板を得た。
[Preparation of hydrophilicity evaluation sample]
The polycarbonate plate {76 mm, 26 mm, 1.0 mm; washed with ethanol} was immersed in a treatment liquid (surface hydrophilic agent), the polycarbonate plate was taken out, the liquid was drained, and heat treatment was performed at 130 ° C. for 1 hour. A surface antifogging polycarbonate plate was obtained.
〔親水性評価結果〕
接触角測定装置{協和界面化学株式会社、DROP MASTER 500、液適量2μL、測定間隔1000ms、測定回数30回}で、表面改質スライドガラスの表面の任意の5箇所について、接触角(度)を測定し、平均値を算出した。結果を表1に示した。
[Hydrophilicity evaluation result]
With a contact angle measuring device {Kyowa Surface Chemistry Co., Ltd., DROP MASTER 500, liquid appropriate amount 2 μL, measurement interval 1000 ms, number of measurements 30 times}, the contact angle (degree) can be measured at any 5 points on the surface of the surface-modified slide glass. It was measured and the average value was calculated. The results are shown in Table 1.
上記結果から明らかの様に本発明のケイ素化合物を添加した系においては、耐久性が高いことが明らかである。 As is clear from the above results, it is clear that the system to which the silicon compound of the present invention is added has high durability.
本発明のケイ素系化合物から誘導される親水化剤は、プラスチックに対して耐久性が高いため、防犯カメラカバーや車のヘッドランプ用カバーに使用可能で、安価に製造出来るため、親水化剤のみならず、帯電防止剤、たんぱく質や血液の付着防止剤として好適である。 Since the hydrophilizing agent derived from the silicon-based compound of the present invention has high durability against plastics, it can be used for security camera covers and car headlamp covers, and can be manufactured at low cost. However, it is suitable as an antistatic agent and an antistatic agent for proteins and blood.
本発明者らは、鋭意研究を重ねた結果、耐久性の高いベタイン系親水化剤を得るために必要なブロックイソシアネート基含有ケイ素化合物を見出し、下記に示す発明を完成させた。
本発明のケイ素系化合物は、
〔1〕 プラスチック用親水化剤の成分が、下記式(1)で表されるブロックイソシアネート基含有ケイ素系化合物であるプラスチック用親水化剤の成分。
(X1)3−o−Si(CH3)o−(CH2)p−S−CH2CHYCOO(CH2)q(OCH2CH2)rNHCO−Z (1)
{式中X1は炭素数1〜6のアルコキシ基、ハロゲン原子及び水酸基であり、oは0又は1であり、pは2〜4の整数であり、Yはメチル基又は水素原子であり、qは2又は3であり、rは0又は1であり、Zは3,5−ジメチルピラゾール基又はメチルエチルケトオキシム基である}
〔2〕 少なくとも前記〔1〕に記載の一般式(1)で表されるブロックイソシアネート基含有ケイ素化合物及びベタイン基含有ケイ素系化合物を含むことを特徴とするプラスチック用親水化剤。
〔3〕 前記ブロックイソシアネート基含有ケイ素化合物の分子鎖が、ベタイン基含有ケイ素系化合物の分子鎖よりも長いことを特徴とする前記〔2〕に記載のプラスチック用親水化剤。
As a result of diligent research, the present inventors have found a blocked isocyanate group-containing silicon compound necessary for obtaining a highly durable betaine-based hydrophilic agent, and have completed the invention shown below.
The silicon compound of the present invention is
[1] component plastic hydrophilizing agent, component plastic hydrophilizing agent is a blocked isocyanate group-containing silicon compound represented by the following formula (1).
(X 1) 3-o -Si (CH 3) o - (CH 2) p -S-CH 2 CHYCOO (CH 2) q (OCH 2 CH 2) r NHCO-Z (1)
{In the formula, X 1 is an alkoxy group having 1 to 6 carbon atoms, a halogen atom and a hydroxyl group, o is 0 or 1, p is an integer of 2 to 4 , and Y is a methyl group or a hydrogen atom. q is 2 or 3 , r is 0 or 1, Z is a 3,5-dimethylpyrazole group or a methylethylketooxime group}
[2] A hydrophilic agent for plastics , which comprises at least a blocked isocyanate group-containing silicon compound represented by the general formula (1) described in the above [1] and a betaine group-containing silicon compound.
[3] The hydrophilic agent for plastics according to the above [2], wherein the molecular chain of the blocked isocyanate group-containing silicon compound is longer than the molecular chain of the betaine group-containing silicon compound.
Claims (3)
(X1)3−o−Si(CH3)o−(CH2)p−S−CH2CHYCOO(CH2)q(OCH2CH2)rNHCO−Z (1)
{式中X1は炭素数1〜6のアルコキシ基、ハロゲン原子及び水酸基であり、oは0又は1であり、pは1〜5の整数であり、Yはメチル基又は水素原子であり、qは1〜4の整数であり、rは0又は1であり、Zは3,5−ジメチルピラゾール基又はメチルエチルケトオキシム基である}で表されるケイ素系化合物 The following formula (1)
(X 1) 3-o -Si (CH 3) o - (CH 2) p -S-CH 2 CHYCOO (CH 2) q (OCH 2 CH 2) r NHCO-Z (1)
{In the formula, X 1 is an alkoxy group having 1 to 6 carbon atoms, a halogen atom and a hydroxyl group, o is 0 or 1, p is an integer of 1 to 5, and Y is a methyl group or a hydrogen atom. q is an integer of 1 to 4, r is 0 or 1, and Z is a 3,5-dimethylpyrazole group or a methylethylketooxime group}.
(X1)3−o−Si(CH3)o−(CH2)p−SH (2)
{式中X1、o及びpは請求項1に記載の 一般式(1)と同一である}
下記式(3)で表される化合物
CH2=CYCOO(CH2)q(OCH2CH2)rNHCO−Z (3)
{式中Y、q、r及びZは請求項1に記載の一般式(1)と同一である}
を反応させることを特徴とする請求項1に記載の一般式(1)で表されるブロックイソシアネート基含有ケイ素化合物の製造方法。 Compounds represented by the following formula (2) and (X 1 ) 3-o- Si (CH 3 ) o- (CH 2 ) p- SH (2)
{X 1, o and p in the formula is the same as in formula (1) according to claim 1}
Compound CH 2 represented by the following formula (3) = CYCOO (CH 2 ) q (OCH 2 CH 2 ) r NHCO-Z (3)
{Y, q, r and Z in the formula are the same as the general formula (1) according to claim 1}
The method for producing a blocked isocyanate group-containing silicon compound represented by the general formula (1) according to claim 1, wherein the reaction is carried out.
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