JP6326157B1 - Resin cleaner - Google Patents
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- JP6326157B1 JP6326157B1 JP2017024816A JP2017024816A JP6326157B1 JP 6326157 B1 JP6326157 B1 JP 6326157B1 JP 2017024816 A JP2017024816 A JP 2017024816A JP 2017024816 A JP2017024816 A JP 2017024816A JP 6326157 B1 JP6326157 B1 JP 6326157B1
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- 229920005989 resin Polymers 0.000 title claims abstract description 36
- 239000011347 resin Substances 0.000 title claims abstract description 36
- 229920001225 polyester resin Polymers 0.000 claims abstract description 33
- 239000004645 polyester resin Substances 0.000 claims abstract description 33
- 150000001875 compounds Chemical class 0.000 claims abstract description 17
- 238000000465 moulding Methods 0.000 claims abstract description 16
- 125000003983 fluorenyl group Chemical group C1(=CC=CC=2C3=CC=CC=C3CC12)* 0.000 claims abstract description 13
- 238000004140 cleaning Methods 0.000 claims abstract description 12
- 239000012459 cleaning agent Substances 0.000 claims abstract description 12
- 239000002994 raw material Substances 0.000 claims abstract description 9
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 4
- 238000000034 method Methods 0.000 claims description 4
- 239000000126 substance Substances 0.000 claims description 4
- 238000006664 bond formation reaction Methods 0.000 claims description 3
- 239000007795 chemical reaction product Substances 0.000 claims description 3
- 238000002844 melting Methods 0.000 claims 1
- 230000008018 melting Effects 0.000 claims 1
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 12
- 239000008188 pellet Substances 0.000 description 11
- -1 polypropylene Polymers 0.000 description 9
- 239000003599 detergent Substances 0.000 description 8
- 238000004519 manufacturing process Methods 0.000 description 8
- NUDSREQIJYWLRA-UHFFFAOYSA-N 4-[9-(4-hydroxy-3-methylphenyl)fluoren-9-yl]-2-methylphenol Chemical compound C1=C(O)C(C)=CC(C2(C3=CC=CC=C3C3=CC=CC=C32)C=2C=C(C)C(O)=CC=2)=C1 NUDSREQIJYWLRA-UHFFFAOYSA-N 0.000 description 7
- 239000000463 material Substances 0.000 description 7
- 229920005992 thermoplastic resin Polymers 0.000 description 7
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 6
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 5
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 5
- 238000002347 injection Methods 0.000 description 5
- 239000007924 injection Substances 0.000 description 5
- 238000001746 injection moulding Methods 0.000 description 5
- 239000000155 melt Substances 0.000 description 5
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 description 4
- 239000000654 additive Substances 0.000 description 4
- 125000000217 alkyl group Chemical group 0.000 description 4
- 229920000139 polyethylene terephthalate Polymers 0.000 description 4
- 239000005020 polyethylene terephthalate Substances 0.000 description 4
- 229920000642 polymer Polymers 0.000 description 4
- 239000011342 resin composition Substances 0.000 description 4
- 238000005406 washing Methods 0.000 description 4
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 3
- 239000004743 Polypropylene Substances 0.000 description 3
- 239000004793 Polystyrene Substances 0.000 description 3
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 3
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 3
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 229920001155 polypropylene Polymers 0.000 description 3
- 229920002223 polystyrene Polymers 0.000 description 3
- 229920001634 Copolyester Polymers 0.000 description 2
- YIMQCDZDWXUDCA-UHFFFAOYSA-N [4-(hydroxymethyl)cyclohexyl]methanol Chemical compound OCC1CCC(CO)CC1 YIMQCDZDWXUDCA-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 230000000996 additive effect Effects 0.000 description 2
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 2
- 125000001931 aliphatic group Chemical group 0.000 description 2
- 125000003118 aryl group Chemical group 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- QQVIHTHCMHWDBS-UHFFFAOYSA-N isophthalic acid Chemical compound OC(=O)C1=CC=CC(C(O)=O)=C1 QQVIHTHCMHWDBS-UHFFFAOYSA-N 0.000 description 2
- RXOHFPCZGPKIRD-UHFFFAOYSA-N naphthalene-2,6-dicarboxylic acid Chemical compound C1=C(C(O)=O)C=CC2=CC(C(=O)O)=CC=C21 RXOHFPCZGPKIRD-UHFFFAOYSA-N 0.000 description 2
- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid Chemical compound OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 description 2
- 229920000728 polyester Polymers 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- CXMXRPHRNRROMY-UHFFFAOYSA-N sebacic acid Chemical compound OC(=O)CCCCCCCCC(O)=O CXMXRPHRNRROMY-UHFFFAOYSA-N 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- 239000004094 surface-active agent Substances 0.000 description 2
- 0 *c(cc(cc1)-c(cccc2)c2-c2ccccc2-c(cc2*)ccc2O)c1O Chemical compound *c(cc(cc1)-c(cccc2)c2-c2ccccc2-c(cc2*)ccc2O)c1O 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 239000004594 Masterbatch (MB) Substances 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 241000083869 Polyommatus dorylas Species 0.000 description 1
- 238000012644 addition polymerization Methods 0.000 description 1
- 235000011037 adipic acid Nutrition 0.000 description 1
- 239000001361 adipic acid Substances 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 239000003945 anionic surfactant Substances 0.000 description 1
- 239000002216 antistatic agent Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- CDQSJQSWAWPGKG-UHFFFAOYSA-N butane-1,1-diol Chemical compound CCCC(O)O CDQSJQSWAWPGKG-UHFFFAOYSA-N 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 238000011086 high cleaning Methods 0.000 description 1
- 239000011256 inorganic filler Substances 0.000 description 1
- 229910003475 inorganic filler Inorganic materials 0.000 description 1
- 239000000314 lubricant Substances 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 150000001247 metal acetylides Chemical class 0.000 description 1
- SLCVBVWXLSEKPL-UHFFFAOYSA-N neopentyl glycol Chemical compound OCC(C)(C)CO SLCVBVWXLSEKPL-UHFFFAOYSA-N 0.000 description 1
- 239000002736 nonionic surfactant Substances 0.000 description 1
- 150000002903 organophosphorus compounds Chemical class 0.000 description 1
- 238000005191 phase separation Methods 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 238000006068 polycondensation reaction Methods 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000007493 shaping process Methods 0.000 description 1
- YXZRCLVVNRLPTP-UHFFFAOYSA-J turquoise blue Chemical compound [Na+].[Na+].[Na+].[Na+].[Cu+2].NC1=NC(Cl)=NC(NC=2C=C(NS(=O)(=O)C3=CC=4C(=C5NC=4NC=4[N-]C(=C6C=CC(=CC6=4)S([O-])(=O)=O)NC=4NC(=C6C=C(C=CC6=4)S([O-])(=O)=O)NC=4[N-]C(=C6C=CC(=CC6=4)S([O-])(=O)=O)N5)C=C3)C(=CC=2)S([O-])(=O)=O)=N1 YXZRCLVVNRLPTP-UHFFFAOYSA-J 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Landscapes
- Moulds For Moulding Plastics Or The Like (AREA)
- Detergent Compositions (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
【課題】原料樹脂としてポリエステル樹脂を使用する成形加工機器内部の洗浄に使用する樹脂洗浄剤の提供。【解決手段】式（１）で表されるフルオレン骨格を有する化合物とポリエステル樹脂との溶融混合処理物から成る樹脂洗浄剤。（Ａは、Ｈ又は−（ＣＨ２）ｎ−Ｈ基；ｎは１以上の整数）【選択図】なしDisclosed is a resin cleaning agent used for cleaning the inside of a molding apparatus using a polyester resin as a raw material resin. A resin cleaning agent comprising a melt-mixed product of a compound having a fluorene skeleton represented by the formula (1) and a polyester resin. (A is H or-(CH2) n-H group; n is an integer of 1 or more) [Selection] None
Description
本発明は、樹脂洗浄剤に関し、詳しくは、押出機、射出成形機器などの成形加工機器内部の洗浄に使用する樹脂洗浄剤に関する。 TECHNICAL FIELD The present invention relates to a resin cleaning agent, and more particularly to a resin cleaning agent used for cleaning inside processing equipment such as an extruder and injection molding equipment.
熱可塑性樹脂の成形加工の分野においては、例えば、原料樹脂材料換え、色換えの際、成形加工機器内部の洗浄が行われる。これにより、例えば、材料換えの場合は、前に使用した材料の残留物の排出を効率的に行うことが出来る。また、成形加工機器内部の洗浄は、炭化物を除去して製品品質を確保するためにも行われる。 In the field of thermoplastic resin molding, for example, the inside of the molding machine is cleaned when changing the raw material resin material or changing the color. Thereby, for example, in the case of material change, the residue of the previously used material can be efficiently discharged. In addition, the inside of the molding apparatus is also cleaned to remove carbides and ensure product quality.
従来、上記のような樹脂洗浄剤としては次のような熱可塑性樹脂組成物が知られている（特許文献１）。
「（Ａ）ポリプロピレン１００質量部に対して、
（Ｂ）（Ａ）成分と相溶化しない熱可塑性樹脂０〜５０質量部、
（Ｃ）（Ａ）成分及び（Ｂ）成分を相溶化させるための熱可塑性樹脂０．５〜５０質量部、及び
（Ｄ）アニオン界面活性剤から選ばれる１種以上とノニオン界面活性剤から選ばれる１種以上を含む界面活性剤混合物０．５〜１５質量部を含有する洗浄用の熱可塑性樹脂組成物。」
Conventionally, the following thermoplastic resin compositions are known as the above resin cleaning agents (Patent Document 1).
“(A) 100 parts by mass of polypropylene,
(B) 0 to 50 parts by mass of a thermoplastic resin that is not compatible with the component (A),
(C) 0.5 to 50 parts by mass of thermoplastic resin for compatibilizing component (A) and component (B), and (D) one or more selected from anionic surfactants and nonionic surfactants A cleaning thermoplastic resin composition containing 0.5 to 15 parts by mass of a surfactant mixture containing one or more of the above. "
上記の洗浄用熱可塑性樹脂組成物は、既に提案されていた数多くの洗浄用熱可塑性樹脂組成物の欠点を改良すると共に、洗浄後に続いてポリプロピレンを成形する場合にポリプロピレンへの置換が容易であるとの利点があるとされている。 The above-mentioned washing thermoplastic resin composition improves the drawbacks of many previously proposed washing thermoplastic resin compositions, and can be easily replaced with polypropylene when polypropylene is subsequently molded after washing. It is said that there are advantages.
本発明の目的は、原料樹脂としてポリエステル樹脂を使用する成形加工機器内部の洗浄に使用する新規な樹脂洗浄剤を提供することにある。 An object of the present invention is to provide a novel resin cleaner used for cleaning the inside of a molding apparatus that uses a polyester resin as a raw material resin.
本発明者は、上記の目的を達成すべく鋭意検討した結果、透明性、高屈折率などの特性故に光機能性原料として良く知られているフルオレン骨格を有する化合物を巧みに利用することにより上記の目的を達成し得るとの知見を得た。 As a result of intensive studies to achieve the above object, the present inventor has successfully used the compound having a fluorene skeleton well known as a photofunctional raw material due to properties such as transparency and high refractive index. The knowledge that the purpose of this can be achieved was obtained.
すなわち、本発明の要旨は、原料樹脂としてポリエステル樹脂を使用する成形加工機器内部の洗浄に使用する樹脂洗浄剤であって、以下に記載の一般式（１）で表されるフルオレン骨格を有する化合物と基材ポリエステル樹脂との溶融混合処理で得られるエステル結合形成反応物から成ることを特徴とする樹脂洗浄剤に存する。 That is, the gist of the present invention is a resin cleaner used for cleaning the inside of a molding apparatus using a polyester resin as a raw material resin, and a compound having a fluorene skeleton represented by the following general formula (1) And a resin detergent characterized by comprising an ester bond-forming reaction product obtained by melt-mixing treatment with a base polyester resin.
（化学式（１）中のＡは、水素原子または−（ＣＨ２）ｎ−Ｈ基であり、ここでｎは１以上の整数を表す。）
(A in the chemical formula (1) is a hydrogen atom or a — (CH 2 ) n —H group, where n represents an integer of 1 or more.)
本発明によれば前記の目的が達成される。 According to the present invention, the above object is achieved.
以下、本発明を詳細に説明する。 Hereinafter, the present invention will be described in detail.
先ず、本発明で使用する前記の一般式（１）で表されるフルオレン骨格を有する化合物について説明する。 First, the compound having a fluorene skeleton represented by the general formula (1) used in the present invention will be described.
一般式（１）中のＡが水素原子で表される化合物はビスフェノールフルオレン（ＢＰＦＬ）であり、メチル基で表される化合物はビスクレゾールフルオレン（ＢＣＦ）である。これらの化合物は光機能性原料として良く知られている。本発明において、前記の化合物において、２個の水酸基が重要であり、化学式（１）中のＡは、水素原子、メチル基の他、任意の炭素数のアルキル基、例えば炭素数６以下の低級アルキル基であってもよく、ポリエチレン鎖であってもよい。これらは直鎖構造であっても分岐構造であってもよい。容易に入手できるのはＢＰＦＬ又はＢＣＦである。ポリエチレン鎖は例えばＢＣＦのメチル基にポリエチレンを付加重合させることにより得ることが可能である。因に、前記の一般式（１）で表されるフルオレン骨格を有する化合物は、その骨格故に耐熱性に優れる。 The compound in which A in the general formula (1) is a hydrogen atom is bisphenolfluorene (BPFL), and the compound represented by a methyl group is biscresol fluorene (BCF). These compounds are well known as photofunctional raw materials. In the present invention, two hydroxyl groups are important in the above compound, and A in the chemical formula (1) is a hydrogen atom, a methyl group, or an alkyl group having any carbon number, for example, a lower group having 6 or less carbon atoms. It may be an alkyl group or a polyethylene chain. These may have a linear structure or a branched structure. Easily available are BPFL or BCF. The polyethylene chain can be obtained, for example, by addition polymerization of polyethylene to the methyl group of BCF. Incidentally, the compound having the fluorene skeleton represented by the general formula (1) is excellent in heat resistance because of the skeleton.
本発明の樹脂洗浄剤は、前記の一般式（１）で表されるフルオレン骨格を有する化合物と基材ポリエステル樹脂との溶融混合処理で得られるエステル結合形成反応物から成る。ここで使用する樹脂洗浄剤の基材として使用されるポリエステル樹脂は、汎用のポリエステル樹脂であり、例えば、原料樹脂材料換えの際に行われる成形加工機器内部の洗浄の場合は、通常、洗浄後に続いて使用するポリエステル樹脂が選択される。 The resin detergent of the present invention comprises an ester bond forming reaction product obtained by a melt mixing treatment of a compound having a fluorene skeleton represented by the general formula (1) and a base polyester resin. The polyester resin used as the base material of the resin cleaning agent used here is a general-purpose polyester resin. For example, in the case of cleaning inside the molding processing equipment performed when changing the raw material resin material, usually after cleaning Subsequently, the polyester resin to be used is selected.
前記のポリエステル樹脂はホモポリエステルであっても共重合ポリエステルであってもよい。ホモポリエステルの場合、芳香族ジカルボン酸と脂肪族グリコールとを重縮合させて得られるものが好ましい。芳香族ジカルボン酸としては、テレフタル酸、２，６−ナフタレンジカルボン酸などが挙げられ、脂肪族グリコールとしては、エチレングリコール、ジエチレングリコール、１，４−シクロヘキサンジメタノール等が挙げられる。代表的なポリエステルとしては、ポリエチレンテレフタレート等が例示される。一方、共重合ポリエステルの場合、ジカルボン酸成分としては、イソフタル酸、フタル酸、テレフタル酸、２，６−ナフタレンジカルボン酸、アジピン酸、セバシン酸、オキシカルボン酸（例えば、ｐ−オキシ安息香酸など）等の一種または二種以上が挙げられ、グリコール成分として、エチレングリコール、ジエチレングリコール、プロピレングリコール、ブタンジオール、４−シクロヘキサンジメタノール、ネオペンチルグリコール等の一種または二種以上が挙げられる。 The polyester resin may be a homopolyester or a copolyester. In the case of a homopolyester, those obtained by polycondensation of an aromatic dicarboxylic acid and an aliphatic glycol are preferred. Examples of the aromatic dicarboxylic acid include terephthalic acid and 2,6-naphthalenedicarboxylic acid, and examples of the aliphatic glycol include ethylene glycol, diethylene glycol, and 1,4-cyclohexanedimethanol. Typical polyester includes polyethylene terephthalate and the like. On the other hand, in the case of copolyester, the dicarboxylic acid component includes isophthalic acid, phthalic acid, terephthalic acid, 2,6-naphthalenedicarboxylic acid, adipic acid, sebacic acid, oxycarboxylic acid (for example, p-oxybenzoic acid, etc.) As the glycol component, one or more of ethylene glycol, diethylene glycol, propylene glycol, butanediol, 4-cyclohexanedimethanol, neopentyl glycol and the like can be mentioned.
前記の一般式（１）で表されるフルオレン骨格を有する化合物の使用量は、基材ポリエステル樹脂に対する割合として、通常１〜３０重量％、好ましくは５〜２０重量％である。 The usage-amount of the compound which has a fluorene skeleton represented by the said General formula (1) is 1-30 weight% normally as a ratio with respect to base polyester resin, Preferably it is 5-20 weight%.
本発明においては、前述の特許文献１に記載の添加剤、例えば、各種の界面活性剤、金属塩、無機フィラー、有機燐化合物などを配合することが出来る。上記の他、滑剤、帯電防止剤なども配合することが出来る。これらの添加剤の配合量は、適宜選択されるが、基材ポリエステル樹脂に対する割合として、通常１〜３０重量％、好ましくは５〜２０重量％である。 In the present invention, additives described in Patent Document 1, for example, various surfactants, metal salts, inorganic fillers, organic phosphorus compounds, and the like can be blended. In addition to the above, a lubricant, an antistatic agent, and the like can also be blended. Although the compounding quantity of these additives is selected suitably, it is 1-30 weight% normally as a ratio with respect to base-material polyester resin, Preferably it is 5-20 weight%.
本発明の樹脂洗浄剤は一般的には次の様にして製造される。すなわち、前記各成分を、ヘンシェルミキサー、タンブラーブレンダー、ニーダー等の混合機で予備混合した後に溶融混合処理する。溶融混合処理は、押出機や、加熱ロール、バンバリーミキサーを使用して行われる。通常、押出機で溶融混合処理してペレット形状に成形される。その大きさは、押出機、射出成形機器などのフィドゾーンの大きさを考慮して適宜選択される。押出機での溶融混合処理の条件は、ポリエステル樹脂ペレットの製造条件として知られている公知の条件を採用すればよい。 The resin cleaner of the present invention is generally produced as follows. That is, each of the above components is premixed by a mixer such as a Henschel mixer, a tumbler blender, or a kneader and then melt mixed. The melt mixing process is performed using an extruder, a heating roll, or a Banbury mixer. Usually, it is formed into pellets by melt mixing with an extruder. The size is appropriately selected in consideration of the size of the feed zone of an extruder, an injection molding machine, or the like. What is necessary is just to employ | adopt the well-known conditions known as manufacturing conditions of a polyester resin pellet as the conditions of the melt mixing process in an extruder.
本発明の樹脂洗浄剤は、原料樹脂としてポリエステル樹脂を使用する成形加工機器内部の洗浄に使用するものであり、しかも、基材としてポリエステル樹脂を使用しているため、成形加工機器内にポリエステル樹脂と異なる樹脂が混入されることがない、すなわち、成形加工機器内部の洗浄に伴う樹脂のコンタミが全くないという大きな利点もある。 The resin cleaning agent of the present invention is used for cleaning the inside of a molding processing apparatus that uses a polyester resin as a raw material resin, and since the polyester resin is used as a base material, the polyester resin is used in the molding processing apparatus. There is also a great advantage that no different resin is mixed, that is, there is no resin contamination accompanying cleaning of the inside of the molding apparatus.
特許文献１記載発明で使用されている相溶化剤は、２種類の高分子材料を混合した樹脂（ポリマアロイ）を作ろうとした際に高分子同士が相分離を起こして均一に混ざり合わない場合に使用される添加剤であり、２種類の高分子の共重合体を形成するための添加剤のことである。 The compatibilizing agent used in the invention described in Patent Document 1 is a case in which when a polymer (polymer alloy) in which two kinds of polymer materials are mixed is made, the polymers cause phase separation and do not mix uniformly. It is an additive used and an additive for forming a copolymer of two kinds of polymers.
従って、本発明の樹脂洗浄剤で使用するフルオレン骨格を有する化合物の作用効果は、従来の相溶化剤とは異なり、次の様に推定される。 Therefore, the effect of the compound having a fluorene skeleton used in the resin detergent of the present invention is estimated as follows, unlike the conventional compatibilizer.
本発明の樹脂洗浄剤の製造時、溶融混合処理により、フルオレン骨格を有する化合物の水酸基（−ＯＨ）と基材ＰＥＴ（ａ）の末端カルボキシル基（−ＣＯＯＨ）とが反応してエステル結合を形成する。そして、分岐構造の形成により相対粘度が低下する。勿論、溶融混合処理時の熱による脱水反応により少量の水が生成してエステル結合が加水分解されるため、フルオレン骨格を有する化合物の水酸基（−ＯＨ）の全量が消失することはない。 During the production of the resin cleaning agent of the present invention, by the melt mixing treatment, the hydroxyl group (—OH) of the compound having a fluorene skeleton reacts with the terminal carboxyl group (—COOH) of the substrate PET (a) to form an ester bond. To do. And relative viscosity falls by formation of a branched structure. Of course, since a small amount of water is generated by the dehydration reaction due to heat during the melt mixing process and the ester bond is hydrolyzed, the total amount of hydroxyl groups (—OH) of the compound having a fluorene skeleton is not lost.
本発明の樹脂洗浄剤の使用時、前記と同様の溶融混合処理により、樹脂洗浄剤は、成形加工機器内部に付着・残留するポリエステル樹脂と溶融混合されつつ移動する。本発明の樹脂洗浄剤の成形加工機器内部の流れは、基材ＰＥＴ（ａ）単独に比し、粘度が低下して良好であり、高い洗浄効果を発揮する。そして、フルオレン骨格を有する化合物の残存水酸基（−ＯＨ）と成形加工機器内部に付着・残留するＰＥＴ（ｂ）の末端カルボキシル基（−ＣＯＯＨ）とが反応（架橋反応）してエステル結合を形成する。この際、前記と同様、分岐構造が形成され、相対粘度は一層低下し、成形加工機器内部からの排出が一層容易となる。なお、上記のカルボキシル基には成形加工機器内部での分解反応によって生じたものも含まれる。 When the resin detergent of the present invention is used, the resin detergent moves while being melt-mixed with the polyester resin adhering and remaining inside the molding apparatus by the same melt mixing treatment as described above. The flow of the resin cleaning agent of the present invention inside the molding apparatus is good with a reduced viscosity as compared with the substrate PET (a) alone, and exhibits a high cleaning effect. Then, the residual hydroxyl group (—OH) of the compound having a fluorene skeleton and the terminal carboxyl group (—COOH) of PET (b) adhering / remaining inside the molding apparatus react to form an ester bond. . At this time, as described above, a branched structure is formed, the relative viscosity is further reduced, and the discharge from the inside of the molding apparatus becomes easier. In addition, what was produced by the decomposition reaction inside a shaping | molding processing apparatus is also contained in said carboxyl group.
なお、前記の一般式（１）で表されるフルオレン骨格を有する化合物のＡがアルキル基またはポリエチレン鎖の場合は、次のようにして耐熱性の改良された樹脂洗浄剤を得ることも出来る。すなわち、樹脂洗浄剤の製造の際に基材ポリエステル樹脂と共にポリスチレンを使用し、水酸基とアルキル基またはポリエチレン鎖により、基材ポリエステル樹脂とポリスチレンとを共重合させ、基材ポリエステル樹脂の耐熱性を高める。具体的には、ポリスチレンは、高温で黄変したり黒色に焼けたりしない特性があるため、高温ではゲル化したり黄変したり黒色に焼けるポリエステル樹脂のこれらの欠点をカバーすることが出来る。 In addition, when A of the compound having a fluorene skeleton represented by the general formula (1) is an alkyl group or a polyethylene chain, a resin detergent having improved heat resistance can be obtained as follows. That is, polystyrene is used together with the base polyester resin in the production of the resin detergent, and the base polyester resin and polystyrene are copolymerized with a hydroxyl group and an alkyl group or a polyethylene chain, thereby increasing the heat resistance of the base polyester resin. . Specifically, since polystyrene has the property that it does not yellow or burn black at high temperatures, it can cover these drawbacks of polyester resins that gel, yellow or burn black at high temperatures.
以下、本発明を実施例より更に詳細に説明するが、本発明はその要旨を超えない限り以下の実施例に限定されるものではない。 EXAMPLES Hereinafter, although this invention is demonstrated further in detail from an Example, this invention is not limited to a following example, unless the summary is exceeded.
［樹脂洗浄剤の製造］
ポリエステル樹脂（三菱化学製商品「ＮＯＶＡＰＥＸ」Ｇ２グレード（固有粘度：０．５９ｄＬ／ｇ）１００重量部にビスクレゾールフルオレン（ＢＣＦ）（ＪＦＥケミカル社製）１０重量部を加え、混合機で予備混合した後、以下に記載の要領で押出機で混練し、射出成形し、ペレット形状の樹脂洗浄剤を得た。ペレットの大きさは、直径３ｍｍ、長さ３ｍｍであった。なお、比較用にＢＣＦを含有しないポリエステル樹脂ペレットも製造した。
[Production of resin cleaner]
10 parts by weight of biscresol fluorene (BCF) (manufactured by JFE Chemical Co.) was added to 100 parts by weight of a polyester resin (Mitsubishi Chemical product “NOVAPEX” G2 grade (inherent viscosity: 0.59 dL / g)) and premixed with a mixer. Thereafter, the mixture was kneaded with an extruder and injection molded in the manner described below to obtain a pellet-shaped resin cleaning agent having a diameter of 3 mm and a length of 3 mm. Polyester resin pellets that do not contain any are also produced.
（押出条件)
押出機；（株）池貝社製「ＰＣＭ４５」（スクリュー径４６ｍｍ）
射出条件；スクリュー回転数１８４ｒｐｍ
温度条件；３００℃
（射出成形条件)
射出成型機；（株）名機製作所製「Ｍ−１００Ｃ」
射出条件；スクリュー回転数８０ｒｐｍ、射出速度５０％、射出圧１０ＭＰＡ、背圧０ＭＰＡ
温度条件；２９０℃
(Extrusion conditions)
Extruder: “PCM45” (screw diameter 46 mm) manufactured by Ikegai Co., Ltd.
Injection conditions: Screw rotation speed 184rpm
Temperature condition: 300 ° C
(Injection molding conditions)
Injection molding machine; “M-100C” manufactured by Meiki Seisakusho Co., Ltd.
Injection conditions: Screw rotation speed 80rpm, injection speed 50%, injection pressure 10MPA, back pressure 0MPA
Temperature condition: 290 ° C
［樹脂洗浄剤の評価］
前記と同じ条件を採用した着色ポリエステル樹脂ペレットの製造工程における押出機と射出成型機の洗浄を行った。着色ポリエステル樹脂ペレットの製造においては、前記と同一のポリエステル樹脂と、これに対して１０重量％の樹脂用着色剤（日本ピグメント社製のポリエステル用マスターバッチターコイズブルー）とを使用した。
[Evaluation of resin cleaner]
The extruder and the injection molding machine were washed in the manufacturing process of colored polyester resin pellets employing the same conditions as described above. In the production of the colored polyester resin pellets, the same polyester resin as described above and 10% by weight of a resin colorant (polyester masterbatch turquoise blue manufactured by Nippon Pigment) were used.
着色ポリエステル樹脂ペレットの製造後、押出機への供給を樹脂洗浄剤ペレットに切り換え、無色のポリエステル樹脂ペレットが得られるまで連続供給し、洗浄に必要な供給量を求めた（実施例１）。比較のため、上記と同様に、着色ポリエステル樹脂ペレットの製造後、押出機への供給をＢＣＦを含有しないポリエステル樹脂ペレットに切り換え、無色のポリエステル樹脂ペレットが得られるまで連続供給し、洗浄に必要な供給量を求めた（比較例１）。比較例１の場合の洗浄に必要な供給量は、実施例１に対して約２倍量であった。 After the production of the colored polyester resin pellets, the supply to the extruder was switched to the resin detergent pellets, which were continuously supplied until colorless polyester resin pellets were obtained, and the supply amount required for cleaning was determined (Example 1). For comparison, in the same manner as above, after the production of colored polyester resin pellets, the supply to the extruder is switched to polyester resin pellets containing no BCF, and it is continuously supplied until colorless polyester resin pellets are obtained, which is necessary for washing. The supply amount was determined (Comparative Example 1). The supply amount necessary for cleaning in the case of Comparative Example 1 was about twice that of Example 1.
Claims (1)
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| JP2017024816A JP6326157B1 (en) | 2017-02-14 | 2017-02-14 | Resin cleaner |
| CN201880010871.8A CN110268016B (en) | 2017-02-14 | 2018-01-25 | Resin cleaning agent and method for melt molding polyester resin |
| KR1020197023049A KR20190111982A (en) | 2017-02-14 | 2018-01-25 | Resin cleaner and melt molding method of polyester resin |
| PCT/JP2018/002226 WO2018150837A1 (en) | 2017-02-14 | 2018-01-25 | Resin cleaning agent and method for melt molding polyester resin |
| TW107104470A TW201840704A (en) | 2017-02-14 | 2018-02-08 | Resin cleaning agent and method for melt molding polyester resin |
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS59124999A (en) * | 1983-01-05 | 1984-07-19 | 大日精化工業株式会社 | Detergent composition for molding machine |
| JP2011144344A (en) * | 2009-03-31 | 2011-07-28 | Osaka Gas Co Ltd | Plasticizer for cellulose derivative |
| JP2015071770A (en) * | 2014-11-11 | 2015-04-16 | 大阪瓦斯株式会社 | Cellulose resin composition |
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS59124999A (en) * | 1983-01-05 | 1984-07-19 | 大日精化工業株式会社 | Detergent composition for molding machine |
| JP2011144344A (en) * | 2009-03-31 | 2011-07-28 | Osaka Gas Co Ltd | Plasticizer for cellulose derivative |
| JP2015071770A (en) * | 2014-11-11 | 2015-04-16 | 大阪瓦斯株式会社 | Cellulose resin composition |
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