JP4925622B2 - Silicone softener - Google Patents
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- JP4925622B2 JP4925622B2 JP2005228668A JP2005228668A JP4925622B2 JP 4925622 B2 JP4925622 B2 JP 4925622B2 JP 2005228668 A JP2005228668 A JP 2005228668A JP 2005228668 A JP2005228668 A JP 2005228668A JP 4925622 B2 JP4925622 B2 JP 4925622B2
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- 229920001296 polysiloxane Polymers 0.000 title claims description 116
- 150000001875 compounds Chemical class 0.000 claims description 22
- 125000003277 amino group Chemical group 0.000 claims description 20
- 125000001841 imino group Chemical group [H]N=* 0.000 claims description 17
- 125000001183 hydrocarbyl group Chemical group 0.000 claims description 14
- FALRKNHUBBKYCC-UHFFFAOYSA-N 2-(chloromethyl)pyridine-3-carbonitrile Chemical compound ClCC1=NC=CC=C1C#N FALRKNHUBBKYCC-UHFFFAOYSA-N 0.000 claims description 11
- -1 alkylene carbonate compound Chemical class 0.000 claims description 11
- 125000004432 carbon atom Chemical group C* 0.000 claims description 11
- 229940014800 succinic anhydride Drugs 0.000 claims description 11
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 10
- 125000000217 alkyl group Chemical group 0.000 claims description 7
- VZCYOOQTPOCHFL-OWOJBTEDSA-N Fumaric acid Chemical compound OC(=O)\C=C\C(O)=O VZCYOOQTPOCHFL-OWOJBTEDSA-N 0.000 claims description 6
- 150000002762 monocarboxylic acid derivatives Chemical class 0.000 claims description 6
- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid Chemical compound OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 claims description 6
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 claims description 6
- 239000004593 Epoxy Substances 0.000 claims description 5
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 claims description 5
- 230000009257 reactivity Effects 0.000 claims description 5
- 239000004215 Carbon black (E152) Substances 0.000 claims description 4
- 150000008064 anhydrides Chemical class 0.000 claims description 4
- 229930195733 hydrocarbon Natural products 0.000 claims description 4
- BJEPYKJPYRNKOW-REOHCLBHSA-N (S)-malic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O BJEPYKJPYRNKOW-REOHCLBHSA-N 0.000 claims description 3
- FEWJPZIEWOKRBE-JCYAYHJZSA-N Dextrotartaric acid Chemical compound OC(=O)[C@H](O)[C@@H](O)C(O)=O FEWJPZIEWOKRBE-JCYAYHJZSA-N 0.000 claims description 3
- LGRFSURHDFAFJT-UHFFFAOYSA-N Phthalic anhydride Natural products C1=CC=C2C(=O)OC(=O)C2=C1 LGRFSURHDFAFJT-UHFFFAOYSA-N 0.000 claims description 3
- KDYFGRWQOYBRFD-UHFFFAOYSA-N Succinic acid Natural products OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 claims description 3
- FEWJPZIEWOKRBE-UHFFFAOYSA-N Tartaric acid Natural products [H+].[H+].[O-]C(=O)C(O)C(O)C([O-])=O FEWJPZIEWOKRBE-UHFFFAOYSA-N 0.000 claims description 3
- 125000001931 aliphatic group Chemical group 0.000 claims description 3
- 125000003545 alkoxy group Chemical group 0.000 claims description 3
- BJEPYKJPYRNKOW-UHFFFAOYSA-N alpha-hydroxysuccinic acid Natural products OC(=O)C(O)CC(O)=O BJEPYKJPYRNKOW-UHFFFAOYSA-N 0.000 claims description 3
- KDYFGRWQOYBRFD-NUQCWPJISA-N butanedioic acid Chemical compound O[14C](=O)CC[14C](O)=O KDYFGRWQOYBRFD-NUQCWPJISA-N 0.000 claims description 3
- JHIWVOJDXOSYLW-UHFFFAOYSA-N butyl 2,2-difluorocyclopropane-1-carboxylate Chemical compound CCCCOC(=O)C1CC1(F)F JHIWVOJDXOSYLW-UHFFFAOYSA-N 0.000 claims description 3
- 239000001530 fumaric acid Substances 0.000 claims description 3
- 150000002430 hydrocarbons Chemical group 0.000 claims description 3
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 3
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 claims description 3
- 239000011976 maleic acid Substances 0.000 claims description 3
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 claims description 3
- 239000001630 malic acid Substances 0.000 claims description 3
- 235000011090 malic acid Nutrition 0.000 claims description 3
- 235000002906 tartaric acid Nutrition 0.000 claims description 3
- 239000011975 tartaric acid Substances 0.000 claims description 3
- 238000006243 chemical reaction Methods 0.000 description 47
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 30
- WFDIJRYMOXRFFG-UHFFFAOYSA-N Acetic anhydride Chemical compound CC(=O)OC(C)=O WFDIJRYMOXRFFG-UHFFFAOYSA-N 0.000 description 18
- 229920000742 Cotton Polymers 0.000 description 15
- 239000002736 nonionic surfactant Substances 0.000 description 15
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 14
- 229910001873 dinitrogen Inorganic materials 0.000 description 14
- 229940079593 drug Drugs 0.000 description 14
- 239000003814 drug Substances 0.000 description 14
- 239000004744 fabric Substances 0.000 description 13
- 238000002845 discoloration Methods 0.000 description 12
- 238000010521 absorption reaction Methods 0.000 description 11
- 239000000835 fiber Substances 0.000 description 10
- 238000010438 heat treatment Methods 0.000 description 10
- 238000000034 method Methods 0.000 description 10
- 239000003795 chemical substances by application Substances 0.000 description 9
- 230000000052 comparative effect Effects 0.000 description 9
- 239000004753 textile Substances 0.000 description 8
- 238000004383 yellowing Methods 0.000 description 8
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 description 7
- CTKINSOISVBQLD-UHFFFAOYSA-N Glycidol Chemical compound OCC1CO1 CTKINSOISVBQLD-UHFFFAOYSA-N 0.000 description 7
- 239000000203 mixture Substances 0.000 description 7
- 229920000728 polyester Polymers 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- 238000001816 cooling Methods 0.000 description 4
- 235000014113 dietary fatty acids Nutrition 0.000 description 4
- 229930195729 fatty acid Natural products 0.000 description 4
- 239000000194 fatty acid Substances 0.000 description 4
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 4
- 239000004902 Softening Agent Substances 0.000 description 3
- 125000000129 anionic group Chemical group 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 239000003995 emulsifying agent Substances 0.000 description 3
- 238000011156 evaluation Methods 0.000 description 3
- 150000004665 fatty acids Chemical class 0.000 description 3
- 230000003405 preventing effect Effects 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 125000002947 alkylene group Chemical group 0.000 description 2
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 238000007598 dipping method Methods 0.000 description 2
- 239000000839 emulsion Substances 0.000 description 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 2
- 238000009472 formulation Methods 0.000 description 2
- 239000004615 ingredient Substances 0.000 description 2
- 150000007524 organic acids Chemical class 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- RUOJZAUFBMNUDX-UHFFFAOYSA-N propylene carbonate Chemical compound CC1COC(=O)O1 RUOJZAUFBMNUDX-UHFFFAOYSA-N 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 229920002994 synthetic fiber Polymers 0.000 description 2
- 239000012209 synthetic fiber Substances 0.000 description 2
- 238000010998 test method Methods 0.000 description 2
- ZZXUZKXVROWEIF-UHFFFAOYSA-N 1,2-butylene carbonate Chemical compound CCC1COC(=O)O1 ZZXUZKXVROWEIF-UHFFFAOYSA-N 0.000 description 1
- PPMCFKAXXHZLMX-UHFFFAOYSA-N 1,3-dioxocan-2-one Chemical compound O=C1OCCCCCO1 PPMCFKAXXHZLMX-UHFFFAOYSA-N 0.000 description 1
- VMSIYTPWZLSMOH-UHFFFAOYSA-N 2-(dodecoxymethyl)oxirane Chemical compound CCCCCCCCCCCCOCC1CO1 VMSIYTPWZLSMOH-UHFFFAOYSA-N 0.000 description 1
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 1
- 244000025254 Cannabis sativa Species 0.000 description 1
- 235000012766 Cannabis sativa ssp. sativa var. sativa Nutrition 0.000 description 1
- 235000012765 Cannabis sativa ssp. sativa var. spontanea Nutrition 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- 239000004677 Nylon Substances 0.000 description 1
- 229920000297 Rayon Polymers 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- 125000003342 alkenyl group Chemical group 0.000 description 1
- 125000000732 arylene group Chemical group 0.000 description 1
- 235000009120 camo Nutrition 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 235000005607 chanvre indien Nutrition 0.000 description 1
- 239000007810 chemical reaction solvent Substances 0.000 description 1
- 150000001805 chlorine compounds Chemical class 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 230000008094 contradictory effect Effects 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 125000002704 decyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 238000004649 discoloration prevention Methods 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 125000003438 dodecyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 238000005108 dry cleaning Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 230000001804 emulsifying effect Effects 0.000 description 1
- 239000002657 fibrous material Substances 0.000 description 1
- 239000011487 hemp Substances 0.000 description 1
- 125000004836 hexamethylene group Chemical group [H]C([H])([*:2])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[*:1] 0.000 description 1
- 125000004051 hexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 230000001771 impaired effect Effects 0.000 description 1
- 230000005764 inhibitory process Effects 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- YHLVIDQQTOMBGN-UHFFFAOYSA-N methyl prop-2-enyl carbonate Chemical compound COC(=O)OCC=C YHLVIDQQTOMBGN-UHFFFAOYSA-N 0.000 description 1
- 125000001421 myristyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 239000004745 nonwoven fabric Substances 0.000 description 1
- 229920001778 nylon Polymers 0.000 description 1
- 125000002347 octyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000001117 oleyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])/C([H])=C([H])\C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 235000005985 organic acids Nutrition 0.000 description 1
- 125000000913 palmityl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 230000000149 penetrating effect Effects 0.000 description 1
- 125000001147 pentyl group Chemical group C(CCCC)* 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 229920000098 polyolefin Polymers 0.000 description 1
- 150000007519 polyprotic acids Polymers 0.000 description 1
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- 125000001424 substituent group Chemical group 0.000 description 1
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- 125000002948 undecyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 150000004670 unsaturated fatty acids Chemical class 0.000 description 1
- 235000021122 unsaturated fatty acids Nutrition 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 210000002268 wool Anatomy 0.000 description 1
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Description
本発明は、繊維製品用のシリコーン系柔軟仕上剤に関する。本発明は、特に、繊維製品に付与した場合に柔軟性、吸水性に優れ、黄変などの変色の問題もなく、併用薬剤との相溶性などの処理浴安定性にも優れるシリコーン系柔軟仕上剤に関する。 The present invention relates to a silicone softener for textile products. In particular, the present invention provides a silicone-based flexible finish that is excellent in flexibility and water absorption when applied to a textile product, has no problem of discoloration such as yellowing, and has excellent treatment bath stability such as compatibility with a concomitant drug. It relates to the agent.
従来、繊維加工の分野においては、柔軟性、平滑性、撥水性等のシリコーンの特性を利用した様々なシリコーン系繊維処理剤が用いられてきた。各種繊維材料の柔軟加工においては、アミノ基および／またはイミノ基を少なくとも２個含有するオルガノポリシロキサン（以下、アミノ変性シリコーンと記す）が、その独特な風合（柔軟性および伸縮性に優れる）と耐久性（耐洗濯性および耐ドライクリーニング性）の観点から、広く用いられている。しかし、アミノ変性シリコーンには加熱による黄変あるいは変色の問題がある。これは分子中のアミノ基が熱によって変化しやすいために起こるもので、白物では黄変、色物では変色といったトラブルとなって現れ、商品価値を下げることになる。また、アミノ変性シリコーンには処理浴の安定性に欠けるという欠点もある。この欠点は、アミノ変性シリコーンをエマルジョンの形態にして用いて繊維を処理する際に、処理浴に加わる物理的衝撃等により処理浴の安定性が崩れてオイルの分離またはガム状物を発生させるものである。この現象は、シリコーン系柔軟仕上剤全般にみられるものであるが、特にアミノ変性シリコーンの場合に多く発生し、これはアミノ基の反応性が大きいことに起因するものであると推察される。また、アミノ変性シリコーンは、処理浴に併用する他の加工薬剤やあるいは処理する生地等に付着して混入してくる物質（例えば、酸、アルカリ、無機塩、界面活性剤、多塩基酸等）との相溶性が、ジメチルシリコーンなどに比較して劣るため、前記したオイル状またはガム状の物質が加工する素材または機械に付着蓄積してトラブルとなることが多かった。特に、綿織物あるいはポリエステル／綿織物等の連続仕上加工においては、形態安定加工処方や染料併用によるシェーディング加工処方に代表されるように、併用薬剤が多く、また加工スピードも速いことから、使用するアミノ変性シリコーンに対しては様々な併用薬剤との相溶性、耐衝撃安定性が要求されており、年々その要求が高度化しているのが現状である。 Conventionally, in the field of fiber processing, various silicone fiber treatment agents that utilize silicone properties such as flexibility, smoothness, and water repellency have been used. In the flexible processing of various fiber materials, organopolysiloxane (hereinafter referred to as amino-modified silicone) containing at least two amino groups and / or imino groups has a unique texture (excellent flexibility and stretchability). And from the viewpoint of durability (washing resistance and dry cleaning resistance). However, amino-modified silicone has a problem of yellowing or discoloration due to heating. This occurs because the amino group in the molecule is easily changed by heat. It appears as a trouble such as yellowing in a white product and discoloration in a colored product, which lowers the commercial value. Amino-modified silicones also have the disadvantage that the treatment bath lacks stability. This disadvantage is that when the fiber is treated with amino-modified silicone in the form of emulsion, the stability of the treatment bath is lost due to physical impact applied to the treatment bath, and oil separation or gum is generated. It is. This phenomenon is observed in general silicone-based soft finishes, but occurs frequently particularly in the case of amino-modified silicone, which is presumed to be caused by the high reactivity of amino groups. In addition, amino-modified silicone is a substance that adheres to and mixes with other processing agents used in the treatment bath or the cloth to be treated (for example, acids, alkalis, inorganic salts, surfactants, polybasic acids, etc.). Therefore, the oily or gum-like substances often adhere to and accumulate on the material or machine to be processed, resulting in troubles. In particular, in continuous finishing of cotton fabric or polyester / cotton fabric, there are many concomitant drugs and the processing speed is high, as represented by the form-stable processing formulation and the shading processing formulation using dyes. Silicone is required to have compatibility with various concomitant drugs and impact resistance stability, and the demand is increasing year by year.
このようなアミノ変性シリコーンが保有する様々な問題を改良するために種々の方法が検討されており、例えば、アミノ変性シリコーンのアミノ基を有機酸、有機酸無水物または有機酸塩化物によってアシル化する方法が提案されている（特許文献１）。しかし、この方法では、アミノ変性シリコーンによる変色の問題や処理浴の安定性に関する欠点を改良することはできたが、アミノ変性シリコーンが持つ独特の風合が損なわれることになった。さらには、アミノ変性シリコーンが持つ独特の風合を保持しながら前記の問題点を改良する方法として、アミノ変性シリコーンとエポキシシランとを反応させる方法が提案されている（特許文献２、特許文献３）が、様々な併用薬剤との相溶性、耐衝撃安定性という点においてはまだ十分に満足できるものではなかった。 Various methods have been studied to improve various problems possessed by such amino-modified silicones. For example, amino groups of amino-modified silicones are acylated with organic acids, organic acid anhydrides or organic acid chlorides. A method to do this has been proposed (Patent Document 1). However, although this method can improve the problem of discoloration due to amino-modified silicone and the drawbacks related to the stability of the treatment bath, the unique texture of amino-modified silicone is impaired. Furthermore, as a method for improving the above-mentioned problems while maintaining the unique texture of amino-modified silicone, a method of reacting amino-modified silicone with epoxysilane has been proposed (Patent Documents 2 and 3). However, it was still not fully satisfactory in terms of compatibility with various concomitant drugs and impact resistance stability.
本発明は、繊維製品に付与した場合にアミノ変性シリコーンが持つ独特の風合を保持しながら、吸水性にも優れ、変色の問題を生じることがなく、様々な併用薬剤との相溶性、耐衝撃安定性などの処理浴安定性を十分に満足させることのできる、シリコーン系柔軟仕上剤を提供することを目的とする。 The present invention retains the unique texture of amino-modified silicone when applied to textile products, while also being excellent in water absorption, causing no discoloration problem, compatible with various concomitant drugs, An object of the present invention is to provide a silicone-based soft finish capable of sufficiently satisfying treatment bath stability such as impact stability.
本発明者らは、上記課題を解決するために鋭意検討を重ねた結果、アミノ変性シリコーンのアミノ基またはイミノ基と反応性を有する特定の化合物を２種以上反応させることにより、繊維製品に適用したときにアミノ変性シリコーンの特徴である優れた柔軟性を保持しながら、吸水性にも優れ、黄変や変色の問題を生じることがなく、その一方で処理浴での併用薬剤との相溶性および処理浴安定性を満足するという、アミノ変性シリコーンに要求される相反する性能を両立させることのできるシリコーン系柔軟仕上剤を提供できることを見出し、この知見に基づいて本発明を完成させた。 As a result of intensive studies to solve the above problems, the present inventors have applied it to textile products by reacting two or more specific compounds having reactivity with amino groups or imino groups of amino-modified silicone. While maintaining the excellent flexibility characteristic of amino-modified silicones, it also has excellent water absorption and does not cause yellowing or discoloration problems, while being compatible with concomitant drugs in treatment baths. In addition, the present inventors have found that it is possible to provide a silicone-based soft finish capable of satisfying the contradictory performance required for amino-modified silicones, which satisfies the treatment bath stability, and has completed the present invention based on this finding.
すなわち、本発明は、下記一般式（１） That is, the present invention provides the following general formula (1)
下記一般式（１）
で示される１分子中にアミノ基および／またはイミノ基を少なくとも２個含有するアミノ変性シリコーンと、アミノ基またはイミノ基と反応性を有する下記の（Ｂ）成分の化合物および下記の（Ａ）成分、（Ｃ）成分および（Ｄ）成分からなる群から選ばれる少なくとも１種の成分の化合物とを、前記アミノ基またはイミノ基の一部もしくは全部について反応させたオルガノポリシロキサン誘導体を含有することを特徴とするシリコーン系柔軟仕上剤。
（Ａ）モノカルボン酸、モノカルボン酸無水物またはモノカルボン酸塩化物
（Ｂ）マレイン酸、無水マレイン酸、フマル酸、リンゴ酸、コハク酸、無水コハク酸、酒石酸、フタル酸または無水フタル酸
（Ｃ）下記一般式（２）
で示されるアルキレンカーボネート化合物
（Ｄ）下記一般式（３）
で示されるエポキシ化合物。
The following general formula (1)
An amino-modified silicone containing at least two amino groups and / or imino groups in one molecule, a compound of the following component (B) having reactivity with the amino group or imino group, and the following component (A) An organopolysiloxane derivative obtained by reacting at least one component compound selected from the group consisting of the component (C) and the component (D) with a part or all of the amino group or imino group. Characteristic silicone softener.
(A) Monocarboxylic acid, monocarboxylic anhydride or monocarboxylic acid chloride (B) Maleic acid, maleic anhydride, fumaric acid, malic acid, succinic acid, succinic anhydride, tartaric acid, phthalic acid or phthalic anhydride ( C) The following general formula (2)
An alkylene carbonate compound (D) represented by the following general formula (3)
An epoxy compound represented by
［式中、Ｒ３は水素原子または炭素数１〜４の脂肪族アルキル基を表す］
で示されるアルキレンカーボネート化合物
（Ｄ）下記一般式（３）
[Wherein R 3 represents a hydrogen atom or an aliphatic alkyl group having 1 to 4 carbon atoms]
An alkylene carbonate compound (D) represented by the following general formula (3)
［式中、Ｒ４は水素原子または一価炭化水素基を表す］
で示されるエポキシ化合物
[Wherein R 4 represents a hydrogen atom or a monovalent hydrocarbon group]
Epoxy compound represented by
本発明のシリコーン系柔軟仕上剤は、繊維製品に付与したときにアミノ変性シリコーンの特徴である優れた柔軟性を保持しながら、黄変や変色を生じず、吸水性を阻害することもなく、また処理浴の安定性や併用薬剤との相溶性にも優れるものであり、アミノ変性シリコーン系の柔軟仕上剤に要求される相反する性能を高いレベルで両立させることができ、より高品質で安定な加工を可能にする。 The silicone-based soft finish of the present invention retains the excellent flexibility that is characteristic of amino-modified silicone when applied to textiles, does not cause yellowing or discoloration, and does not inhibit water absorption. It also has excellent treatment bath stability and compatibility with concomitant drugs, and can achieve a high level of conflicting performance required for amino-modified silicone-based soft finishes. Can be processed easily.
以下、本発明の好ましい形態について説明するが、これは本発明の好ましい実施の態様を説明するためのものであって、本発明はこれらの態様のみに限定されるものではないことを理解されたい。 Hereinafter, preferred embodiments of the present invention will be described. However, this is for explaining preferred embodiments of the present invention, and it should be understood that the present invention is not limited to these embodiments. .
本発明は、前記一般式（１）で示される１分子中にアミノ基および／またはイミノ基を少なくとも２個含有するアミノ変性シリコーンと、アミノ基またはイミノ基と反応性を有する前記（Ａ）〜（Ｄ）からなる群から選ばれる２種以上の化合物とを、前記アミノ基またはイミノ基の一部もしくは全部について反応させたオルガノポリシロキサン誘導体を含有することを特徴とするシリコーン系柔軟仕上剤である。 The present invention relates to an amino-modified silicone containing at least two amino groups and / or imino groups in one molecule represented by the general formula (1), and the aforementioned (A) to (A) to (A) to A silicone-based soft finish comprising an organopolysiloxane derivative obtained by reacting two or more compounds selected from the group consisting of (D) with a part or all of the amino group or imino group. is there.
本発明に用いる前記一般式（１）のアミノ変性シリコーンとしては、アミノ基および／またはイミノ基を少なくとも２個含有するものであればよく、直鎖状であっても分岐鎖を有していてもよい。また、末端はトリオルガノシロキサンの構造であっても、あるいは他の置換基が付加されていてもよい。式（１）中のＲ１は、炭素数１〜５の一価炭化水素基であり、例えば、メチル基、エチル基、プロピル基、ブチル基、ペンチル基が挙げられ、１分子中のＲ１はすべて同一であっても、相異なっていてもよく、一般にはＲ１はメチル基であるのが好ましいけれども、メチル基と上記した他の基との組み合わせであってもよい。式（１）中のＲ２は、水素原子または一価炭化水素基であり、一価炭化水素基としては、例えば、メチル基、エチル基、プロピル基、フェニル基が挙げられる。また、式（１）中のＡは、炭素数１〜５の一価炭化水素基、水酸基、アルコキシ基または−Ｑ−（ＮＨＣＨ２ＣＨ２）ａＮＨＲ２であり、Ａが２個とも−Ｑ−（ＮＨＣＨ２ＣＨ２）ａＮＨＲ２の場合には、ｎが０となることも可能である。式(１)中のＱは、二価炭化水素基であり、例えば、−ＣＨ２−、−ＣＨ２−ＣＨ２−、−ＣＨ２−ＣＨ２−ＣＨ２−、−ＣＨ２−ＣＨ（ＣＨ３）−ＣＨ２−、−（ＣＨ２）４−のようなアルキレン基、−（ＣＨ２）２Ｃ６Ｈ４−のようなアルキレンアリーレン基が挙げられる。 The amino-modified silicone of the general formula (1) used in the present invention may be any one that contains at least two amino groups and / or imino groups. Even if it is linear, it has a branched chain. Also good. Moreover, the terminal may be a triorganosiloxane structure, or another substituent may be added. R 1 in formula (1) is a monovalent hydrocarbon group having 1 to 5 carbon atoms, and examples thereof include a methyl group, an ethyl group, a propyl group, a butyl group, and a pentyl group, and R 1 in one molecule. May be the same or different from each other. In general, R 1 is preferably a methyl group, but may be a combination of a methyl group and the other groups described above. R 2 in Formula (1) is a hydrogen atom or a monovalent hydrocarbon group, and examples of the monovalent hydrocarbon group include a methyl group, an ethyl group, a propyl group, and a phenyl group. Also, the A in the formula (1), the monovalent hydrocarbon group having 1 to 5 carbon atoms, a hydroxyl group, an alkoxy group or -Q- (NHCH 2 CH 2) a a NHR 2, A is also 2 -Q In the case of — (NHCH 2 CH 2 ) a NHR 2 , n can be 0. Q in the formula (1) is a divalent hydrocarbon radical, for example, -CH 2 -, - CH 2 -CH 2 -, - CH 2 -CH 2 -CH 2 -, - CH 2 -CH (CH 3 ) alkylene groups such as —CH 2 — and — (CH 2 ) 4 — and alkylene arylene groups such as — (CH 2 ) 2 C 6 H 4 —.
ｍ＋ｎは少なくとも１０であり、ｍ＋ｎが１０未満の場合には柔軟性の付与効果が乏しく、また１０００を超えるとオルガノポリシロキサン誘導体を乳化しにくくなるため、好ましくは１００〜１０００である。さらに、ｍ／（ｎ＋２）＝５〜５００であり、この値が５未満の場合には柔軟性の付与効果が乏しく、５００を超えると伸縮性の付与効果が乏しくなる。 m + n is at least 10, and when m + n is less than 10, the effect of imparting flexibility is poor, and when it exceeds 1000, the organopolysiloxane derivative becomes difficult to emulsify, and is preferably 100 to 1000. Furthermore, m / (n + 2) = 5 to 500. When this value is less than 5, the effect of imparting flexibility is poor, and when it exceeds 500, the effect of imparting elasticity becomes poor.
本発明に用いる一般式（１）のアミノ変性シリコーンは、アミノ基および／またはイミノ基を少なくとも２個含有し、−Ｑ−（ＮＨＣＨ２ＣＨ２）ａＮＨＲ２を１分子中に２個以上含有することが好ましい。−Ｑ−（ＮＨＣＨ２ＣＨ２）ａＮＨＲ２が１個であるとエポキシ化合物による架橋反応が十分に行えない傾向にある。そして、この基［−Ｑ−（ＮＨＣＨ２ＣＨ２）ａＮＨＲ２］は、前記一般式（１）に示すとおり、側鎖に存在していても、分子の末端に存在していてもよく、またその両方に存在していてもよい。さらに、一般式（１）のアミノ変性シリコーンは、その２５℃における粘度が１０〜１０万センチストークス（ｃＳｔ）の範囲にあるのが好ましい。 The amino-modified silicone of the general formula (1) used in the present invention contains at least two amino groups and / or imino groups, and contains two or more -Q- (NHCH 2 CH 2 ) a NHR 2 in one molecule. It is preferable to do. When -Q- (NHCH 2 CH 2 ) a NHR 2 is 1, there is a tendency that a crosslinking reaction with an epoxy compound cannot be sufficiently performed. And this group [—Q— (NHCH 2 CH 2 ) a NHR 2 ] may be present in the side chain or at the end of the molecule as shown in the general formula (1), It may also exist in both. Furthermore, the amino-modified silicone of the general formula (1) preferably has a viscosity at 25 ° C. in the range of 100,000 to 100,000 centistokes (cSt).
本発明のシリコーン系柔軟仕上剤は、前記一般式（１）で示されるアミノ変性シリコーンと、アミノ基またはイミノ基と反応性を有する前記（Ａ）〜（Ｄ）からなる群から選ばれる２種以上の化合物とを、前記アミノ基またはイミノ基の一部若しくは全部について反応させたオルガノポリシロキサン誘導体を含有するものである。 The silicone softener of the present invention is selected from the group consisting of the amino-modified silicone represented by the general formula (1) and the above-mentioned (A) to (D) having reactivity with an amino group or imino group. It contains an organopolysiloxane derivative obtained by reacting the above compound with part or all of the amino group or imino group.
本発明に用いる（Ａ）成分のモノカルボン酸としては、例えば、炭素数１〜２０の脂肪酸が挙げられ、脂肪酸は飽和脂肪酸であっても、不飽和脂肪酸であってもよい。また、モノカルボン酸無水物またはモノカルボン酸塩化物としては、例えば、炭素数１〜８の直鎖状のアルキル基を有する脂肪酸の無水物または塩化物が挙げられ、好ましくは炭素数１〜５の直鎖状のアルキル基を有する脂肪酸の無水物または塩化物である。 As monocarboxylic acid of (A) component used for this invention, a C1-C20 fatty acid is mentioned, for example, A fatty acid may be a saturated fatty acid or an unsaturated fatty acid. Examples of monocarboxylic acid anhydrides or monocarboxylic acid chlorides include anhydrides or chlorides of fatty acids having a linear alkyl group having 1 to 8 carbon atoms, preferably 1 to 5 carbon atoms. It is an anhydride or chloride of a fatty acid having a linear alkyl group.
本発明に用いる（Ｂ）成分の化合物としては、マレイン酸、無水マレイン酸、フマル酸、リンゴ酸、コハク酸、無水コハク酸、酒石酸、フタル酸または無水フタル酸が挙げられる。 As the compound of component (B) used in the present invention, Ma maleic acid, maleic anhydride, fumaric acid, malic acid, succinic acid, succinic anhydride, tartaric acid, phthalic acid or phthalic anhydride.
また、本発明に用いる（Ｃ）成分の前記一般式（２）で示されるアルキレンカーボネート化合物としては、例えば、エチレンカーボネート、プロピレンカーボネート、イソブチレンカーボネート、１，２−ブチレンカーボネート、ペンチレンカーボネート、へキシレンカーボネートなどが挙げられる。 Examples of the alkylene carbonate compound represented by the general formula (2) of the component (C) used in the present invention include ethylene carbonate, propylene carbonate, isobutylene carbonate, 1,2-butylene carbonate, pentylene carbonate, and hexylene. Examples include carbonate.
さらに、本発明に用いる（Ｄ）成分の前記一般式（３）で示されるエポキシ化合物において、式中のＲ４は水素原子または一価炭化水素基であり、一価炭化水素基としては、例えば、ブチル基、ヘキシル基、オクチル基、デシル基、ウンデシル基、ラウリル基、ミリスチル基、セチル基のような直鎖アルキル基、または２−エチルヘキシル基、イソデシル基、イソトリデシル基のような分岐状アルキル基、オレイル基のようなアルケニル基が挙げられる。 Furthermore, in the epoxy compound represented by the general formula (3) of the component (D) used in the present invention, R 4 in the formula is a hydrogen atom or a monovalent hydrocarbon group. Examples of the monovalent hydrocarbon group include: , Butyl group, hexyl group, octyl group, decyl group, undecyl group, lauryl group, myristyl group, linear alkyl group such as cetyl group, or branched alkyl group such as 2-ethylhexyl group, isodecyl group, isotridecyl group And an alkenyl group such as an oleyl group.
本発明において、前記一般式（１）で示されるアミノ変性シリコーンと前記（Ａ）〜（Ｄ）成分との反応は、いずれの（Ａ）〜（Ｄ）成分についても、通常の方法で行うことができる。例えば、アミノ変性シリコーンと（Ａ）成分との反応においては、アミノ変性シリコーンと（Ａ）成分を室温で反応容器に仕込み、窒素ガス気流下で加熱昇温し、５０〜１２０℃の温度範囲で反応させることが望ましい。同様に、アミノ変性シリコーンと（Ｂ）成分との反応においては１００〜１５０℃の温度範囲で反応させるのが望ましく、アミノ変性シリコーンと（Ｃ）成分との反応においては７０〜１４０℃の温度範囲で反応させるのが望ましく、アミノ変性シリコーンと（Ｄ）成分との反応においては７０〜１１０℃の温度範囲で反応させるのが望ましい。また、アミノ変性シリコーンと、（Ａ）〜（Ｄ）成分からなる群から選ばれる２種以上の化合物との反応の際には、前記反応温度の範囲内であれば、アミノ変性シリコーンと２種以上の化合物とを同時に反応させてもよいし、前記アミノ基またはイミノ基と各成分との反応率を確認しながら順次反応させてもよい。 In the present invention, the reaction between the amino-modified silicone represented by the general formula (1) and the components (A) to (D) is carried out by any ordinary method for any of the components (A) to (D). Can do. For example, in the reaction between the amino-modified silicone and the component (A), the amino-modified silicone and the component (A) are charged in a reaction vessel at room temperature, heated and heated in a nitrogen gas stream, and in a temperature range of 50 to 120 ° C. It is desirable to react. Similarly, the reaction between the amino-modified silicone and the component (B) is preferably carried out in the temperature range of 100 to 150 ° C., and the reaction between the amino-modified silicone and the component (C) is in the temperature range of 70 to 140 ° C. The reaction between the amino-modified silicone and the component (D) is preferably carried out in the temperature range of 70 to 110 ° C. In addition, when the amino-modified silicone is reacted with two or more compounds selected from the group consisting of the components (A) to (D), the amino-modified silicone and the two compounds are within the reaction temperature range. The above compounds may be reacted simultaneously, or may be reacted sequentially while confirming the reaction rate between the amino group or imino group and each component.
また、（Ａ）〜（Ｄ）成分の組み合わせ、及び、反応率を調整することにより、本発明のオルガノポリシロキサン誘導体を含有するシリコーン系柔軟仕上剤の風合、吸水性、変色防止性、併用薬剤との併用性、機械安定性などの性能を制御することが可能となる。特に、アニオン系薬剤などの併用薬剤との相溶性、処理浴の安定性を高めるには、（Ｂ）成分を必須成分とした形で、（Ａ）成分、（Ｃ）成分または（Ｄ）成分との組み合わせを選択するのが好ましい。 Further, by adjusting the combination of the components (A) to (D) and the reaction rate, the texture, water absorption, discoloration prevention property, combined use of the silicone-based soft finish containing the organopolysiloxane derivative of the present invention It becomes possible to control performances such as compatibility with drugs and mechanical stability. In particular, in order to increase the compatibility with a concomitant drug such as an anionic drug and the stability of the treatment bath, the component (B) is an essential component, the component (A), the component (C) or the component (D). It is preferable to select a combination.
本発明においては、アミノ変性シリコーンと反応させる（Ａ）〜（Ｄ）成分からなる群から選ばれる２種以上の化合物のそれぞれの使用量比については、選ばれる化合物の種類やアミノ基またはイミノ基に対する反応度合いにより異なり一概にはいえないが、２種の化合物の場合には選ばれた各成分をそれぞれ１０〜９０質量％使用することが好ましく、３種以上の場合には選ばれた各成分をそれぞれ２〜８０質量％使用することが好ましい。そして、本発明においては、これらの各成分とアミノ変性シリコーンとの反応の際には、反応溶媒や触媒の使用は特に必要としない。 In the present invention, the usage ratio of each of the two or more compounds selected from the group consisting of the components (A) to (D) to be reacted with the amino-modified silicone is the kind of the compound selected, the amino group or the imino group. Depending on the degree of reaction with respect to the compound, it cannot be generally stated, but in the case of two kinds of compounds, it is preferable to use 10 to 90% by mass of each of the selected ingredients, and in the case of three or more kinds, each of the selected ingredients It is preferable to use 2 to 80% by mass of each. In the present invention, it is not particularly necessary to use a reaction solvent or a catalyst in the reaction of each of these components with the amino-modified silicone.
本発明のシリコーン系柔軟仕上剤は、上記反応により得られたオルガノポリシロキサン誘導体を有機溶剤に溶解した溶剤系のシリコーン系柔軟仕上剤として得るか、あるいはオルガノポリシロキサン誘導体を乳化剤を用いて水に乳化・分散させた水系のシリコーン系柔軟仕上剤として得ることができる。一般には、乳化・分散液とした水系のシリコーン系柔軟仕上剤とするのが好ましい。前記オルガノポリシロキサン誘導体を乳化・分散させる際に使用する乳化剤としては、非イオン界面活性剤を組み合わせて用いることが好ましく、組み合わせた乳化剤のＨＬＢ（グリフィン）の平均値が１０〜１５であることが好ましい。 The silicone softener of the present invention is obtained as a solvent-based silicone softener obtained by dissolving the organopolysiloxane derivative obtained by the above reaction in an organic solvent, or the organopolysiloxane derivative is made into water using an emulsifier. It can be obtained as an emulsified and dispersed aqueous silicone softener. In general, it is preferable to use an aqueous silicone softening agent as an emulsion / dispersion. The emulsifier used when emulsifying and dispersing the organopolysiloxane derivative is preferably used in combination with a nonionic surfactant, and the combined emulsifier has an HLB (Griffin) average value of 10 to 15. preferable.
本発明のシリコーン系柔軟仕上剤を繊維製品に付与するに際しては、上記の溶剤系のシリコーン系柔軟仕上剤を有機溶剤で溶解した希釈溶液にして付与するか、あるいは上記の水系のシリコーン系柔軟仕上剤を水で希釈したに乳化・分散液で付与することができる。 In applying the silicone-based soft finish of the present invention to a textile product, the above-mentioned solvent-based silicone soft finish is applied as a diluted solution dissolved in an organic solvent, or the above-mentioned aqueous silicone-based soft finish is used. The agent can be applied with an emulsified / dispersed solution after diluted with water.
また、本発明のシリコーン系柔軟仕上剤を付与する繊維製品の種類および形態には制限はなく、繊維の種類としては木綿、麻、羊毛、絹などの天然繊維、ポリエステル、ナイロン、アクリル、ポリオレフィンなどの合成繊維、アセテートなどの半合成繊維、ベンベルグ、レーヨンなどの再生繊維およびこれらの複合繊維が挙げられ、繊維製品の形態としては糸、織物、編物、不織布などが挙げられる。 Moreover, there is no restriction | limiting in the kind and form of the fiber product which provides the silicone type soft finish of this invention, As a kind of fiber, natural fibers, such as cotton, hemp, wool, silk, polyester, nylon, acrylic, polyolefin, etc. Synthetic fibers, semi-synthetic fibers such as acetate, regenerated fibers such as Bemberg and rayon, and composite fibers thereof. Examples of fiber products include yarns, woven fabrics, knitted fabrics, and non-woven fabrics.
本発明のシリコーン系柔軟仕上剤を前記繊維製品に付与する方法にも制限はなく、従来から行われている浸漬法、パッド法等を用いればよく、そしてその処理浴の濃度は、浸漬法の場合には前記オルガノポリシロキサン誘導体の濃度が０．０５〜３％ｏ．ｗ．ｆ．であるのが好ましく、パッド法の場合には前記オルガノポリシロキサン誘導体の濃度が０．０１〜３％ｓｏｌｎであるのが好ましい。また、繊維に対する付着量は、前記オルガノポリシロキサン誘導体が０．０１〜３質量％になるように付与することが好ましい。 The method for applying the silicone softener of the present invention to the textile product is not limited, and a conventional dipping method, pad method, etc. may be used, and the concentration of the treatment bath is the same as that of the dipping method. In this case, the concentration of the organopolysiloxane derivative is 0.05 to 3% o. w. f. In the case of the pad method, the concentration of the organopolysiloxane derivative is preferably 0.01 to 3% soln. Moreover, it is preferable to give the adhesion amount with respect to a fiber so that the said organopolysiloxane derivative may be 0.01-3 mass%.
さらに、本発明のシリコーン系柔軟仕上剤と処理浴で併用する薬剤としては、樹脂加工剤、消泡剤、浸透剤、スリップ防止剤、強度低下防止剤、他の柔軟剤などが挙げられる。 Furthermore, as a chemical | medical agent used together with the silicone type softness finishing agent of this invention, and a processing bath, a resin processing agent, an antifoamer, a penetrating agent, an anti-slip agent, an intensity | strength fall prevention agent, another softening agent, etc. are mentioned.
以下、実施例により本発明をさらに具体的に説明するが、本発明はこれらの実施例により何ら制限されるものではない。 EXAMPLES Hereinafter, although an Example demonstrates this invention further more concretely, this invention is not restrict | limited at all by these Examples.
なお、実施例中の部および％はそれぞれ質量部および質量％を示し、粘度は２５℃における値である。 In addition, the part and% in an Example show a mass part and the mass%, respectively, and a viscosity is a value in 25 degreeC.
実施例１
下記式（４）で表される１２００センチストークスの粘度を有するアミノ変性シリコーン１５０部および無水酢酸４部を反応容器に仕込み、窒素ガス気流下で加熱昇温し、１００〜１１０℃の温度で約１時間反応させた後、無水コハク酸４部を仕込み、さらに加熱昇温し、１２０〜１３０℃の温度で約２時間反応させた。反応終了後冷却し、非イオン界面活性剤のソフタノール５０（(株)日本触媒製、ＨＬＢ＝１０．５）１７部、ソフタノール９０（(株)日本触媒製、ＨＬＢ＝１３．３）２８部、ソフタノール１２０（(株)日本触媒製、ＨＬＢ＝１４．５）４０部、水７５７部を加えて乳化させ、安定性のよいシリコーン系柔軟仕上剤を得た。
Example 1
150 parts of amino-modified silicone having a viscosity of 1200 centistokes represented by the following formula (4) and 4 parts of acetic anhydride are charged into a reaction vessel, heated and heated in a nitrogen gas stream, and about 100 to 110 ° C. After reacting for 1 hour, 4 parts of succinic anhydride was added, the temperature was further raised by heating, and the reaction was carried out at a temperature of 120 to 130 ° C. for about 2 hours. After completion of the reaction, the mixture was cooled and 17 parts of nonionic surfactant Softanol 50 (manufactured by Nippon Shokubai Co., Ltd., HLB = 10.5), softener 90 (manufactured by Nippon Shokubai Co., Ltd., HLB = 13.3) 28 parts, 40 parts of Softanol 120 (manufactured by Nippon Shokubai Co., Ltd., HLB = 14.5) and 757 parts of water were added and emulsified to obtain a silicone-based soft finish with good stability.
実施例２（参考例）
実施例１で用いたものと同じアミノ変性シリコーン１５０部、無水酢酸４部およびエチレンカーボネート８部を反応容器に仕込み、窒素ガス気流下で加熱昇温し、１００〜１１０℃の温度で約２時間反応させた。反応終了後冷却し、非イオン界面活性剤のソフタノール５０（(株)日本触媒製）１７部、ソフタノール９０（(株)日本触媒製）２８部、ソフタノール１２０（(株)日本触媒製）４０部、水７５３部を加えて乳化させ、安定性のよいシリコーン系柔軟仕上剤を得た。
Example 2 (Reference Example)
150 parts of the same amino-modified silicone as used in Example 1, 4 parts of acetic anhydride and 8 parts of ethylene carbonate were charged into a reaction vessel, heated under a nitrogen gas stream, and heated at a temperature of 100 to 110 ° C. for about 2 hours. Reacted. Cooled after the reaction, 17 parts of nonionic surfactant Softanol 50 (made by Nippon Shokubai Co., Ltd.), 28 parts of Softanol 90 (made by Nippon Shokubai Co., Ltd.), 40 parts of Softanol 120 (made by Nippon Shokubai Co., Ltd.) Then, 753 parts of water was added and emulsified to obtain a stable silicone softener.
実施例３（参考例）
実施例１で用いたものと同じアミノ変性シリコーン１５０部および無水酢酸４部を反応容器に仕込み、窒素ガス気流下で加熱昇温し、１００〜１１０℃の温度で約１時間反応させた後、下記式（５）で表されるグリシドール３部を仕込み、９０〜１００℃の温度で約１時間反応させた。反応終了後冷却し、非イオン界面活性剤のソフタノール５０（(株)日本触媒製）１７部、ソフタノール９０（(株)日本触媒製）２８部、ソフタノール１２０（(株)日本触媒製）４０部、水７５８部を加えて乳化させ、安定性のよいシリコーン系柔軟仕上剤を得た。
Example 3 (Reference Example)
150 parts of the same amino-modified silicone and 4 parts of acetic anhydride as used in Example 1 were charged into a reaction vessel, heated and heated under a nitrogen gas stream, and reacted at a temperature of 100 to 110 ° C. for about 1 hour. 3 parts of glycidol represented by the following formula (5) was charged and reacted at a temperature of 90 to 100 ° C. for about 1 hour. Cooled after the reaction, 17 parts of nonionic surfactant Softanol 50 (made by Nippon Shokubai Co., Ltd.), 28 parts of Softanol 90 (made by Nippon Shokubai Co., Ltd.), 40 parts of Softanol 120 (made by Nippon Shokubai Co., Ltd.) Then, 758 parts of water was added and emulsified to obtain a silicone-type soft finish with good stability.
実施例４
実施例１で用いたものと同じアミノ変性シリコーン１５０部およびエチレンカーボネート８部を反応容器に仕込み、窒素ガス気流下で加熱昇温し、１００〜１１０℃の温度で約２時間反応させた後、無水コハク酸４部を仕込み、さらに加熱昇温し、１２０〜１３０℃の温度で約１時間反応させた。反応終了後冷却し、非イオン界面活性剤のソフタノール５０（(株)日本触媒製）１７部、ソフタノール９０（(株)日本触媒製）２８部、ソフタノール１２０（(株)日本触媒製）４０部、水７５３部を加えて乳化させ、安定性のよいシリコーン系柔軟仕上剤を得た。
Example 4
150 parts of the same amino-modified silicone and 8 parts of ethylene carbonate used in Example 1 were charged into a reaction vessel, heated and heated under a nitrogen gas stream, and reacted at a temperature of 100 to 110 ° C. for about 2 hours. 4 parts of succinic anhydride was added, the temperature was further raised by heating, and the reaction was carried out at a temperature of 120 to 130 ° C. for about 1 hour. Cooled after the reaction, 17 parts of nonionic surfactant Softanol 50 (made by Nippon Shokubai Co., Ltd.), 28 parts of Softanol 90 (made by Nippon Shokubai Co., Ltd.), 40 parts of Softanol 120 (made by Nippon Shokubai Co., Ltd.) Then, 753 parts of water was added and emulsified to obtain a stable silicone softener.
実施例５（参考例）
実施例１で用いたものと同じアミノ変性シリコーン１５０部およびエチレンカーボネート８部を反応容器に仕込み、窒素ガス気流下で加熱昇温し、１００〜１１０℃の温度で約２時間反応させた後、９０℃まで冷却した。その後、グリシドール３部を仕込み、９０〜１００℃の温度で約１時間反応させた。反応終了後冷却し、非イオン界面活性剤のソフタノール５０（(株)日本触媒製）１７部、ソフタノール９０（(株)日本触媒製）２８部、ソフタノール１２０（(株)日本触媒製）４０部、水７５４部を加えて乳化させ、安定性のよいシリコーン系柔軟仕上剤を得た。
Example 5 (Reference Example)
150 parts of the same amino-modified silicone and 8 parts of ethylene carbonate used in Example 1 were charged into a reaction vessel, heated and heated under a nitrogen gas stream, and reacted at a temperature of 100 to 110 ° C. for about 2 hours. Cooled to 90 ° C. Thereafter, 3 parts of glycidol was charged and reacted at a temperature of 90 to 100 ° C. for about 1 hour. Cooled after the reaction, 17 parts of nonionic surfactant Softanol 50 (made by Nippon Shokubai Co., Ltd.), 28 parts of Softanol 90 (made by Nippon Shokubai Co., Ltd.), 40 parts of Softanol 120 (made by Nippon Shokubai Co., Ltd.) 754 parts of water was added and emulsified to obtain a silicone-based soft finish with good stability.
実施例６
実施例１で用いたものと同じアミノ変性シリコーン１５０部および下記式（６）で表されるラウリルグリシジルエーテル１２部を反応容器に仕込み、窒素ガス気流下で加熱昇温し、９０〜１００℃の温度で約２時間反応させた。その後、無水コハク酸４部を仕込み、さらに加熱昇温し、１２０〜１３０℃の温度で約１時間反応させた。反応終了後冷却し、非イオン界面活性剤のソフタノール５０（(株)日本触媒製）１７部、ソフタノール９０（(株)日本触媒製）２８部、ソフタノール１２０（(株)日本触媒製）４０部、水７４９部を加えて乳化させ、安定性のよいシリコーン系柔軟仕上剤を得た。
Example 6
150 parts of the same amino-modified silicone as used in Example 1 and 12 parts of lauryl glycidyl ether represented by the following formula (6) were charged into a reaction vessel, heated to a temperature in a nitrogen gas stream, and heated at 90 to 100 ° C. The reaction was carried out at temperature for about 2 hours. Thereafter, 4 parts of succinic anhydride was charged, the temperature was further raised, and the reaction was carried out at a temperature of 120 to 130 ° C. for about 1 hour. Cooled after the reaction, 17 parts of nonionic surfactant Softanol 50 (made by Nippon Shokubai Co., Ltd.), 28 parts of Softanol 90 (made by Nippon Shokubai Co., Ltd.), 40 parts of Softanol 120 (made by Nippon Shokubai Co., Ltd.) 749 parts of water was added and emulsified to obtain a silicone-type soft finish with good stability.
実施例７
実施例１で用いたものと同じアミノ変性シリコーン１５０部及び無水酢酸４部を反応容器に仕込み、窒素ガス気流下で加熱昇温し、１００〜１１０℃の温度で約１時間反応させた後、無水コハク酸４部を仕込み、更に加熱昇温し、１２０〜１３０℃の温度で約１時間反応させた。その後９０℃まで冷却してグリシドール３部を仕込み、９０〜１００℃の温度で約１時間反応させた。反応終了後冷却し、非イオン界面活性剤のソフタノール５０（(株)日本触媒製）１７部、ソフタノール９０（(株)日本触媒製）２８部、ソフタノール１２０（(株)日本触媒製）４０部、水７５４部を加えて乳化させ、安定性のよいシリコーン系柔軟仕上剤を得た。
Example 7
150 parts of the same amino-modified silicone and 4 parts of acetic anhydride as used in Example 1 were charged into a reaction vessel, heated and heated under a nitrogen gas stream, and reacted at a temperature of 100 to 110 ° C. for about 1 hour. 4 parts of succinic anhydride was charged, the temperature was further raised, and the reaction was carried out at a temperature of 120 to 130 ° C. for about 1 hour. Thereafter, the mixture was cooled to 90 ° C., charged with 3 parts of glycidol, and reacted at a temperature of 90 to 100 ° C. for about 1 hour. Cooled after the reaction, 17 parts of nonionic surfactant Softanol 50 (made by Nippon Shokubai Co., Ltd.), 28 parts of Softanol 90 (made by Nippon Shokubai Co., Ltd.), 40 parts of Softanol 120 (made by Nippon Shokubai Co., Ltd.) 754 parts of water was added and emulsified to obtain a silicone-based soft finish with good stability.
実施例８
実施例１で用いたものと同じアミノ変性シリコーン１５０部およびエチレンカーボネート８部を反応容器に仕込み、窒素ガス気流下で加熱昇温し、１００〜１１０℃の温度で約２時間反応させた後、無水コハク酸４部を仕込み、さらに加熱昇温し、１２０〜１３０℃の温度で約１時間反応させた。その後９０℃まで冷却した後、グリシドール３部を仕込み、９０〜１００℃の温度で約１時間反応させた。反応終了後冷却し、非イオン界面活性剤のソフタノール５０（(株)日本触媒製）１７部、ソフタノール９０（(株)日本触媒製）２８部、ソフタノール１２０（(株)日本触媒製）４０部、水７５０部を加えて乳化させ、安定性のよいシリコーン系柔軟仕上剤を得た。
Example 8
150 parts of the same amino-modified silicone and 8 parts of ethylene carbonate used in Example 1 were charged into a reaction vessel, heated and heated under a nitrogen gas stream, and reacted at a temperature of 100 to 110 ° C. for about 2 hours. 4 parts of succinic anhydride was added, the temperature was further raised by heating, and the reaction was carried out at a temperature of 120 to 130 ° C. for about 1 hour. Then, after cooling to 90 ° C., 3 parts of glycidol was charged and reacted at a temperature of 90 to 100 ° C. for about 1 hour. Cooled after the reaction, 17 parts of nonionic surfactant Softanol 50 (made by Nippon Shokubai Co., Ltd.), 28 parts of Softanol 90 (made by Nippon Shokubai Co., Ltd.), 40 parts of Softanol 120 (made by Nippon Shokubai Co., Ltd.) 750 parts of water was added and emulsified to obtain a silicone-based soft finish with good stability.
実施例９
下記式（７）で表される５００センチストークスの粘度を有するアミノ変性シリコーン１５０部およびエチレンカーボネート８部を反応容器に仕込み、窒素ガス気流下で加熱昇温し、１００〜１１０℃の温度で約２時間反応させた後、無水コハク酸４部を仕込み、さらに加熱昇温し、１２０〜１３０℃の温度で約１時間反応させた。その後９０℃まで冷却した後、グリシドール３部を仕込み、９０〜１００℃の温度で約１時間反応させた。反応終了後冷却し、非イオン界面活性剤のソフタノール５０（(株)日本触媒製）１７部、ソフタノール９０（(株)日本触媒製）２８部、ソフタノール１２０（(株)日本触媒製）４０部、水７５０部を加えて乳化させ、安定性のよいシリコーン系柔軟仕上剤を得た。
Example 9
150 parts of amino-modified silicone having a viscosity of 500 centistokes represented by the following formula (7) and 8 parts of ethylene carbonate are charged into a reaction vessel, heated and heated in a nitrogen gas stream, and about 100 to 110 ° C. After reacting for 2 hours, 4 parts of succinic anhydride was added, and the temperature was further raised by heating, followed by reaction at a temperature of 120 to 130 ° C. for about 1 hour. Then, after cooling to 90 ° C., 3 parts of glycidol was charged and reacted at a temperature of 90 to 100 ° C. for about 1 hour. Cooled after the reaction, 17 parts of nonionic surfactant Softanol 50 (made by Nippon Shokubai Co., Ltd.), 28 parts of Softanol 90 (made by Nippon Shokubai Co., Ltd.), 40 parts of Softanol 120 (made by Nippon Shokubai Co., Ltd.) 750 parts of water was added and emulsified to obtain a silicone-based soft finish with good stability.
実施例１０
下記式（８）で表される３５００センチストークスの粘度を有するアミノ変性シリコーン１５０部およびエチレンカーボネート８部を反応容器に仕込み、窒素ガス気流下で加熱昇温し、１００〜１１０℃の温度で約２時間反応させた後、無水コハク酸４部を仕込み、さらに加熱昇温し、１２０〜１３０℃の温度で約１時間反応させた。その後９０℃まで冷却した後、グリシドール３部を仕込み、９０〜１００℃の温度で約１時間反応させた。反応終了後冷却し、非イオン界面活性剤のソフタノール５０（(株)日本触媒製）１７部、ソフタノール９０（(株)日本触媒製）２８部、ソフタノール１２０（(株)日本触媒製）４０部、水７５０部を加えて乳化させ、安定性のよいシリコーン系柔軟仕上剤を得た。
Example 10
150 parts of an amino-modified silicone having a viscosity of 3500 centistokes represented by the following formula (8) and 8 parts of ethylene carbonate are charged into a reaction vessel, heated and heated in a nitrogen gas stream, and about 100 to 110 ° C. After reacting for 2 hours, 4 parts of succinic anhydride was added, and the temperature was further raised by heating, followed by reaction at a temperature of 120 to 130 ° C. for about 1 hour. Then, after cooling to 90 ° C., 3 parts of glycidol was charged and reacted at a temperature of 90 to 100 ° C. for about 1 hour. Cooled after the reaction, 17 parts of nonionic surfactant Softanol 50 (made by Nippon Shokubai Co., Ltd.), 28 parts of Softanol 90 (made by Nippon Shokubai Co., Ltd.), 40 parts of Softanol 120 (made by Nippon Shokubai Co., Ltd.) 750 parts of water was added and emulsified to obtain a silicone-based soft finish with good stability.
実施例１１
実施例１で用いたものと同じアミノ変性シリコーン１５０部及びプロピレンカーボネート９部を反応容器に仕込み、窒素ガス気流下で加熱昇温し、１００〜１１０℃の温度で約２時間反応させた後、無水コハク酸０．３部を仕込み、更に加熱昇温し、１２０〜１３０℃の温度で約１時間反応させた。その後９０℃まで冷却した後、グリシドール３部を仕込み、９０〜１００℃の温度で約１時間反応させた。反応終了後冷却し、非イオン界面活性剤のソフタノール５０（（株）日本触媒製）１７部、ソフタノール９０（（株）日本触媒製）２８部、ソフタノール１２０（（株）日本触媒製）４０部、水７５３部を加えて乳化させ、安定性のよいシリコーン系柔軟仕上剤を得た。
Example 11
After charging 150 parts of the same amino-modified silicone and 9 parts of propylene carbonate used in Example 1 into a reaction vessel, heating and heating under a nitrogen gas stream, and reacting at a temperature of 100 to 110 ° C. for about 2 hours, 0.3 part of succinic anhydride was charged, and the temperature was further raised by heating, and the reaction was carried out at a temperature of 120 to 130 ° C. for about 1 hour. Then, after cooling to 90 ° C., 3 parts of glycidol was charged and reacted at a temperature of 90 to 100 ° C. for about 1 hour. After completion of the reaction, the mixture was cooled and 17 parts of nonionic surfactant Softanol 50 (made by Nippon Shokubai Co., Ltd.), 28 parts of Softanol 90 (made by Nippon Shokubai Co., Ltd.), 40 parts of Softanol 120 (made by Nippon Shokubai Co., Ltd.) Then, 753 parts of water was added and emulsified to obtain a stable silicone softener.
比較例１
実施例１で用いたものと同じアミノ変性シリコーン１５０部を反応させずにそのままで用い、これに実施例１と同様に非イオン界面活性剤のソフタノール５０（(株)日本触媒製）１７部、ソフタノール９０（(株)日本触媒製）２８部、ソフタノール１２０（(株)日本触媒製）４０部、水７６５部を加えて乳化させてシリコーン系柔軟仕上剤を得た。
Comparative Example 1
150 parts of the same amino-modified silicone as used in Example 1 was used as it was without reacting, and 17 parts of non-ionic surfactant Softanol 50 (manufactured by Nippon Shokubai Co., Ltd.) as in Example 1, 28 parts of Softanol 90 (manufactured by Nippon Shokubai Co., Ltd.), 40 parts of Softanol 120 (manufactured by Nippon Shokubai Co., Ltd.) and 765 parts of water were added and emulsified to obtain a silicone soft finish.
比較例２
実施例１で用いたものと同じアミノ変性シリコーン１５０部および無水酢酸６部を反応容器に仕込み、窒素ガス気流下で１００〜１１０℃の温度で約１時間反応させた後冷却し、実施例１と同様に非イオン界面活性剤のソフタノール５０（(株)日本触媒製）１７部、ソフタノール９０（(株)日本触媒製）２８部、ソフタノール１２０（(株)日本触媒製）４０部、水７５９部を加えて乳化させてシリコーン系柔軟仕上剤を得た。
Comparative Example 2
150 parts of the same amino-modified silicone and 6 parts of acetic anhydride as used in Example 1 were charged into a reaction vessel, reacted at a temperature of 100 to 110 ° C. for about 1 hour under a nitrogen gas stream, and then cooled. In the same manner as above, 17 parts of nonionic surfactant Softanol 50 (manufactured by Nippon Shokubai Co., Ltd.), 28 parts of Softanol 90 (manufactured by Nippon Shokubai Co., Ltd.), 40 parts of Softanol 120 (manufactured by Nippon Shokubai Co., Ltd.), water 759 Part was added and emulsified to obtain a silicone soft finish.
比較例３
実施例１で用いたものと同じアミノ変性シリコーン１５０部および無水酢酸４部を反応容器に仕込み、窒素ガス気流下で１００〜１１０℃の温度で約１時間反応させた後、９０℃まで冷却した後、下記式（９）で表されるエポキシシラン５部を仕込み、９０〜１００℃の温度で約１時間反応させた後、実施例１と同様に非イオン界面活性剤のソフタノール５０（(株)日本触媒製）１７部、ソフタノール９０（(株)日本触媒製）２８部、ソフタノール１２０（(株)日本触媒製）４０部、水７５６部を加えて乳化させシリコーン系柔軟仕上剤を得た。
Comparative Example 3
150 parts of the same amino-modified silicone and 4 parts of acetic anhydride as used in Example 1 were charged into a reaction vessel, reacted at a temperature of 100 to 110 ° C. for about 1 hour under a nitrogen gas stream, and then cooled to 90 ° C. Thereafter, 5 parts of an epoxysilane represented by the following formula (9) was charged and reacted at a temperature of 90 to 100 ° C. for about 1 hour, and then the nonionic surfactant Softanol 50 ( ) Nippon Shokubai) 17 parts, Softanol 90 (made by Nippon Shokubai Co., Ltd.) 28 parts, Softanol 120 (made by Nippon Shokubai Co., Ltd.) 40 parts, water 756 parts were added and emulsified to obtain a silicone soft finish. .
以上の実施例および比較例で用いたアミノ変性シリコーンおよび（Ａ）〜（Ｄ）成分をまとめて下記の表１に示す。 The amino-modified silicone and the components (A) to (D) used in the above Examples and Comparative Examples are collectively shown in Table 1 below.
試験例１（浴安定性試験）
以上の実施例および比較例により得られたシリコーン系柔軟仕上剤について、綿織物やポリエステル／綿（Ｔ／Ｃ）織物の連続加工を想定した三段階の処理浴組成で、併用薬剤との相溶性や耐衝撃安定性についての試験を行った。
Test Example 1 (Bath stability test)
The silicone-based softener obtained in the above examples and comparative examples has a three-stage treatment bath composition assuming continuous processing of cotton fabric and polyester / cotton (T / C) fabric. A test for impact resistance stability was conducted.
試験方法
５００ｍＬのビーカーに下記表２に示す浴組成で処理浴３００ｍＬを調製し、この処理浴をホモミキサー（Ｔ．Ｋ．ロボミックス ｆ−ｍｏｄｅｌ（特殊機化工業(株)製）を用いて６０００ｒｐｍで１０分間ミキシング処理した後の浴の状態を観察し、下記の評価基準で評価した結果を下記表３に示す。
Test method A 300 mL treatment bath was prepared in a 500 mL beaker with the bath composition shown in Table 2 below, and this treatment bath was prepared using a homomixer (TK Robotics f-model (manufactured by Tokushu Kika Kogyo Co., Ltd.). The state of the bath after mixing at 6000 rpm for 10 minutes was observed, and the results of evaluation based on the following evaluation criteria are shown in Table 3 below.
○：良好
△：やや不良
×：不良
○: Good △: Somewhat bad ×: Bad
表３の結果からわかるように、本発明に係るシリコーン系柔軟仕上剤は、レベル１（一般的処方）においては併用薬剤との相溶性、耐衝撃安定性とも良好である。特に、（Ｂ）成分の化合物とアミノ変性シリコーンとを反応させたシリコーン系柔軟仕上剤については、様々な併用薬剤を想定した最も厳しい条件であるレベル３の処方においても良好な結果が得られている。これは、アミノ変性シリコーンのアミノ基またはイミノ基と（Ｂ）成分の化合物のジカルボン酸または環状酸無水物との反応により得られたオルガノポリシロキサン誘導体に、アニオン基であるカルボキシル基が一部導入されたことによるものと推定する。このようにアミノ変性シリコーンとジカルボン酸または環状酸無水物とを用いて反応させたアニオン化アミノ変性シリコーンは、アニオン系の併用薬剤との相溶性を飛躍的に向上させるために、特に併用薬剤が多く、加工スピードが速い綿織物、ポリエステル／綿（Ｔ／Ｃ）織物等の連続加工用のシリコーン系柔軟仕上剤として有用である。 As can be seen from the results in Table 3, the silicone softener according to the present invention has good compatibility with the concomitant drugs and impact resistance stability at level 1 (general prescription). In particular, with regard to the silicone-based soft finish obtained by reacting the compound of the component (B) with amino-modified silicone, good results were obtained even in the prescription of level 3, which is the most severe condition assuming various concomitant drugs. Yes. This is because a part of the carboxyl group, which is an anionic group, is introduced into the organopolysiloxane derivative obtained by the reaction of the amino group or imino group of the amino-modified silicone with the dicarboxylic acid or cyclic anhydride of the compound (B). It is presumed that it was due to this. In this way, the anionized amino-modified silicone reacted with an amino-modified silicone and dicarboxylic acid or cyclic acid anhydride is used in order to drastically improve the compatibility with an anionic concomitant drug. It is useful as a silicone-based softening agent for continuous processing, such as cotton fabric and polyester / cotton (T / C) fabric, which have a high processing speed.
試験例２
上記の実施例および比較例のシリコーン系柔軟仕上剤を用いて、柔軟性、熱変色（黄変）性、吸水性についての試験を行った。
Test example 2
Using the silicone-type soft finishes of the above Examples and Comparative Examples, tests for flexibility, thermal discoloration (yellowing), and water absorption were performed.
試験方法
供試布として綿１００％ブロード（綿織物）、ポリエステル／綿（６５／３５）ブロード（Ｔ／Ｃ織物）、綿１００％ニット蛍光布（綿ニット）の３種を用いて、実施例または比較例のシリコーン系柔軟仕上剤の３％ｓｏｌｎの処理浴でパディング処理（１ｄｉｐ−１ｎｉｐ、ピックアップ：綿織物７０％、Ｔ／Ｃ織物７０％、綿ニット：９０％）を行った後、１２０℃で３分間の乾燥、続いて１６０℃で１分間の加熱処理を行った。得られた処理布を以下の評価項目について評価した結果を下記表４に示す。
Test method Examples or three kinds of test cloths: 100% cotton (cotton woven), polyester / cotton (65/35) broad (T / C woven), and 100% cotton knitted fluorescent cloth (cotton knitted) After performing padding treatment (1 dip-1 nip, pickup: 70% cotton fabric, 70% T / C fabric, 90% cotton knit: 90%) in a 3% soln treatment bath of a silicone soft finish of the comparative example, at 120 ° C. Drying for 3 minutes was followed by heat treatment at 160 ° C. for 1 minute. Table 4 below shows the results of evaluating the obtained treated cloth for the following evaluation items.
１．風合：触感にて判定（５：非常に柔軟、４：柔軟、３：やや柔軟、２：やや粗硬、 １：粗硬、およびそれぞれの中間位で評価）
２．白度：ミノルタ製ＣＭ−３７００ｄ測色機にて、綿ニット蛍光布の白度(Ｈ．Ｗ． Ｉ．)を測定。
３．吸水性：ＪＩＳ Ｌ−１０９６ Ａ法に準じて測定。水滴を一滴滴下し、水滴が完 全に消失するまでの時間(秒)を測定。
1. Feel: Judged by tactile sensation (5: Very flexible, 4: Flexible, 3: Slightly flexible, 2: Slightly hard, 1: Slightly hard, and evaluated at intermediate positions)
2. Whiteness: The whiteness (HW I.) of a cotton knit fluorescent cloth was measured with a CM-3700d colorimeter manufactured by Minolta.
3. Water absorption: Measured according to JIS L-1096 A method. A drop of water is dropped and the time (seconds) until the water drops completely disappear is measured.
表４の結果からわかるように、比較例１および２のシリコーン系柔軟仕上剤はアミノ変性シリコーン独特のヌメリ感に富んだ風合を付与できるが、白度の低下、吸水性の阻害が大きいという欠点を有している。また、比較例３のシリコーン系柔軟仕上剤は風合と熱変色防止性（白度）の両立という点でバランスがとれているが、吸水性の阻害がやや大きい。これに対して、実施例のシリコーン系柔軟仕上剤では、風合、熱変色防止性（白度）、吸水性のいずれにおいてもバランス良く良好な結果を示している。 As can be seen from the results in Table 4, the silicone-based soft finishes of Comparative Examples 1 and 2 can give a texture that is rich in the sliminess unique to amino-modified silicones, but the whiteness is reduced and the water absorption is greatly inhibited. Has drawbacks. Further, the silicone-based soft finish of Comparative Example 3 is balanced in terms of the balance between texture and thermal discoloration preventing property (whiteness), but the inhibition of water absorption is somewhat large. On the other hand, the silicone-based soft finishes of the examples show good results in a well-balanced manner in all of the texture, the thermal discoloration preventing property (whiteness) and the water absorption.
本発明のシリコーン系柔軟仕上剤によれば、繊維製品に対して柔軟性と伸縮性に富んだ高級な風合を付与することができ、熱による黄変や変色も起こさず、さらには吸水性にも優れる製品を与える。また、加工時の処理浴における耐衝撃安定性や、併用薬剤との相溶性に優れることから、加工時のガムアップ等のトラブルもなく、安定した柔軟仕上加工が可能となる。したがって、従来のアミノ変性シリコーンによる柔軟性を維持し、熱による黄変や変色を防止し、加工時処理浴の安定性を保持するという、高度化する要求性能に対応することが可能となる。よって、本発明は、産業上有用である。 According to the silicone-based soft finish of the present invention, it is possible to impart a high-quality texture rich in flexibility and stretchability to a textile product, without causing yellowing or discoloration due to heat, and further, water absorption Even give an excellent product. Moreover, since it is excellent in impact resistance stability in the treatment bath during processing and compatibility with the concomitant drug, stable flexible finishing can be performed without troubles such as gum-up during processing. Therefore, it is possible to meet the increasingly demanded performance of maintaining the flexibility of the conventional amino-modified silicone, preventing yellowing and discoloration due to heat, and maintaining the stability of the processing bath during processing. Therefore, the present invention is industrially useful.
Claims (1)
で示される１分子中にアミノ基および／またはイミノ基を少なくとも２個含有するアミノ変性シリコーンと、アミノ基またはイミノ基と反応性を有する下記の（Ｂ）成分の化合物および下記の（Ａ）成分、（Ｃ）成分および（Ｄ）成分からなる群から選ばれる少なくとも１種の成分の化合物とを、前記アミノ基またはイミノ基の一部もしくは全部について反応させたオルガノポリシロキサン誘導体を含有することを特徴とするシリコーン系柔軟仕上剤。
（Ａ）モノカルボン酸、モノカルボン酸無水物またはモノカルボン酸塩化物
（Ｂ）マレイン酸、無水マレイン酸、フマル酸、リンゴ酸、コハク酸、無水コハク酸、酒石酸、フタル酸または無水フタル酸
（Ｃ）下記一般式（２）
で示されるアルキレンカーボネート化合物
（Ｄ）下記一般式（３）
で示されるエポキシ化合物 The following general formula (1)
An amino-modified silicone containing at least two amino groups and / or imino groups in one molecule, a compound of the following component (B) having reactivity with the amino group or imino group, and the following component (A) An organopolysiloxane derivative obtained by reacting at least one component compound selected from the group consisting of the component (C) and the component (D) with a part or all of the amino group or imino group. Characteristic silicone softener.
(A) Monocarboxylic acid, monocarboxylic anhydride or monocarboxylic acid chloride (B) Maleic acid, maleic anhydride, fumaric acid, malic acid, succinic acid, succinic anhydride, tartaric acid, phthalic acid or phthalic anhydride ( C) The following general formula (2)
An alkylene carbonate compound (D) represented by the following general formula (3)
Epoxy compound represented by
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| BR112018072818B8 (en) * | 2016-05-10 | 2022-11-16 | Dow Silicones Corp | SILICONE BLOCK COPOLYMER, PROCESS FOR PREPARING A COPOLYMER, EMULSION, METHOD FOR TREATMENT OF A SUBSTRATE, COMPOSITION FOR PERSONAL CARE, SHAMPOO, CONDITIONER FOR HAIR, AND, ANIDRO COMPOSITION FOR HAIR TREATMENT WITHOUT RINSE |
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