JP6651970B2 - Fiber sizing agent - Google Patents
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- JP6651970B2 JP6651970B2 JP2016087579A JP2016087579A JP6651970B2 JP 6651970 B2 JP6651970 B2 JP 6651970B2 JP 2016087579 A JP2016087579 A JP 2016087579A JP 2016087579 A JP2016087579 A JP 2016087579A JP 6651970 B2 JP6651970 B2 JP 6651970B2
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- 239000000835 fiber Substances 0.000 title claims description 50
- 238000004513 sizing Methods 0.000 title claims description 48
- 239000003795 chemical substances by application Substances 0.000 title claims description 40
- 239000000178 monomer Substances 0.000 claims description 61
- 239000000203 mixture Substances 0.000 claims description 26
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 claims description 15
- 125000003055 glycidyl group Chemical group C(C1CO1)* 0.000 claims description 15
- -1 polyoxyethylene group Polymers 0.000 claims description 14
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 13
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 12
- 125000000217 alkyl group Chemical group 0.000 claims description 8
- 125000004432 carbon atom Chemical group C* 0.000 claims description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 35
- 229920001577 copolymer Polymers 0.000 description 34
- 229920000049 Carbon (fiber) Polymers 0.000 description 14
- 239000004917 carbon fiber Substances 0.000 description 14
- VOZRXNHHFUQHIL-UHFFFAOYSA-N glycidyl methacrylate Chemical compound CC(=C)C(=O)OCC1CO1 VOZRXNHHFUQHIL-UHFFFAOYSA-N 0.000 description 14
- 239000003505 polymerization initiator Substances 0.000 description 13
- 238000006116 polymerization reaction Methods 0.000 description 13
- 230000015572 biosynthetic process Effects 0.000 description 10
- 239000007787 solid Substances 0.000 description 10
- 238000003786 synthesis reaction Methods 0.000 description 10
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 9
- 238000000034 method Methods 0.000 description 9
- 239000003822 epoxy resin Substances 0.000 description 8
- 229920000647 polyepoxide Polymers 0.000 description 8
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 8
- 239000000243 solution Substances 0.000 description 8
- 239000003365 glass fiber Substances 0.000 description 7
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 6
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 6
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- 239000000047 product Substances 0.000 description 6
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 5
- 239000012736 aqueous medium Substances 0.000 description 5
- 239000003960 organic solvent Substances 0.000 description 5
- 239000002904 solvent Substances 0.000 description 5
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 4
- 229920002430 Fibre-reinforced plastic Polymers 0.000 description 4
- 239000003093 cationic surfactant Substances 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 238000011156 evaluation Methods 0.000 description 4
- 239000011151 fibre-reinforced plastic Substances 0.000 description 4
- 238000005227 gel permeation chromatography Methods 0.000 description 4
- 239000011521 glass Substances 0.000 description 4
- 239000012784 inorganic fiber Substances 0.000 description 4
- NOBYOEQUFMGXBP-UHFFFAOYSA-N (4-tert-butylcyclohexyl) (4-tert-butylcyclohexyl)oxycarbonyloxy carbonate Chemical compound C1CC(C(C)(C)C)CCC1OC(=O)OOC(=O)OC1CCC(C(C)(C)C)CC1 NOBYOEQUFMGXBP-UHFFFAOYSA-N 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 3
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 3
- 239000003513 alkali Substances 0.000 description 3
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 3
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 3
- 238000010528 free radical solution polymerization reaction Methods 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 3
- 229920002239 polyacrylonitrile Polymers 0.000 description 3
- YEJRWHAVMIAJKC-UHFFFAOYSA-N 4-Butyrolactone Chemical compound O=C1CCCO1 YEJRWHAVMIAJKC-UHFFFAOYSA-N 0.000 description 2
- 239000004793 Polystyrene Substances 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 230000000996 additive effect Effects 0.000 description 2
- 239000000853 adhesive Substances 0.000 description 2
- 230000001070 adhesive effect Effects 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 238000007598 dipping method Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 230000020169 heat generation Effects 0.000 description 2
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 2
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000011159 matrix material Substances 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- RPQRDASANLAFCM-UHFFFAOYSA-N oxiran-2-ylmethyl prop-2-enoate Chemical compound C=CC(=O)OCC1CO1 RPQRDASANLAFCM-UHFFFAOYSA-N 0.000 description 2
- 229920002223 polystyrene Polymers 0.000 description 2
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 229920005989 resin Polymers 0.000 description 2
- 239000011347 resin Substances 0.000 description 2
- 125000002914 sec-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 2
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 2
- ZVBFXRWQTYTMRU-UHFFFAOYSA-N (1-butylcyclohexyl) carboxyoxy carbonate Chemical compound OC(=O)OOC(=O)OC1(CCCC)CCCCC1 ZVBFXRWQTYTMRU-UHFFFAOYSA-N 0.000 description 1
- ARXJGSRGQADJSQ-UHFFFAOYSA-N 1-methoxypropan-2-ol Chemical compound COCC(C)O ARXJGSRGQADJSQ-UHFFFAOYSA-N 0.000 description 1
- DPGYCJUCJYUHTM-UHFFFAOYSA-N 2,4,4-trimethylpentan-2-yloxy 2-ethylhexaneperoxoate Chemical compound CCCCC(CC)C(=O)OOOC(C)(C)CC(C)(C)C DPGYCJUCJYUHTM-UHFFFAOYSA-N 0.000 description 1
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 description 1
- 239000004925 Acrylic resin Substances 0.000 description 1
- 229920000178 Acrylic resin Polymers 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 1
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 1
- 239000004480 active ingredient Substances 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 239000002518 antifoaming agent Substances 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 230000003078 antioxidant effect Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 238000007865 diluting Methods 0.000 description 1
- 238000010790 dilution Methods 0.000 description 1
- 239000012895 dilution Substances 0.000 description 1
- 239000002270 dispersing agent Substances 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 239000003480 eluent Substances 0.000 description 1
- 238000007720 emulsion polymerization reaction Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 1
- LRDFRRGEGBBSRN-UHFFFAOYSA-N isobutyronitrile Chemical compound CC(C)C#N LRDFRRGEGBBSRN-UHFFFAOYSA-N 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 150000002596 lactones Chemical class 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 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 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- 150000001451 organic peroxides Chemical class 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 229920001515 polyalkylene glycol Polymers 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 230000003449 preventive effect Effects 0.000 description 1
- 238000010526 radical polymerization reaction Methods 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000010557 suspension polymerization reaction Methods 0.000 description 1
- 239000006097 ultraviolet radiation absorber Substances 0.000 description 1
- 239000004846 water-soluble epoxy resin Substances 0.000 description 1
- 238000009941 weaving Methods 0.000 description 1
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
- Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)
Description
本発明は、炭素繊維やガラス繊維などの無機繊維の集束性を向上させる繊維集束剤に関するものである。 TECHNICAL FIELD The present invention relates to a fiber sizing agent for improving sizing of inorganic fibers such as carbon fibers and glass fibers.
高強度かつ高耐久性が要求される自動車や航空機の部材として、エポキシ樹脂などのマトリックス樹脂と、炭素繊維やガラス繊維などの無機繊維とを含む繊維強化プラスチックが使用されている。
前記繊維強化プラスチックに使用される炭素繊維やガラス繊維などの無機繊維は、高強度を付与する観点から、炭素やガラスからなる複数の単繊維が束になった繊維束が使用される。一般的に、この繊維束は、配合した材料の取り扱いや物性を向上させるために、マトリックス樹脂に適合する繊維集束剤を繊維表面に付着させるサイジング処理を施した状態で用いられている。
前記繊維集束剤としては、一般にエポキシ樹脂組成物が使用され、例えば特許文献１には、エポキシ樹脂とカチオン性界面活性剤と水を含有する水分散体からなる水性エポキシ樹脂組成物が繊維処理剤として利用できることが記載されている。
しかし、前記水性エポキシ樹脂組成物は、含有するカチオン性界面活性剤の影響によって接着強さの点が不十分であるため、繊維集束剤として使用しても繊維の集束性という点で十分ではなく、繊維の製織工程で解れや毛羽立ち、糸切れによる生産性の低下や、この組成物を用いて成形された繊維強化プラスチックの強度不足といった問題があった。
2. Description of the Related Art Fiber-reinforced plastics containing a matrix resin such as an epoxy resin and inorganic fibers such as carbon fiber and glass fiber have been used as members for automobiles and aircraft that require high strength and high durability.
As the inorganic fiber such as carbon fiber and glass fiber used for the fiber reinforced plastic, a fiber bundle formed by bundling a plurality of single fibers made of carbon or glass is used from the viewpoint of imparting high strength. Generally, the fiber bundle is used in a state where a sizing treatment for attaching a fiber sizing agent compatible with the matrix resin to the fiber surface is performed in order to improve handling and physical properties of the compounded material.
As the fiber sizing agent, an epoxy resin composition is generally used. For example, Patent Document 1 discloses an aqueous epoxy resin composition comprising an aqueous dispersion containing an epoxy resin, a cationic surfactant and water. It is described that it can be used as.
However, since the aqueous epoxy resin composition has an insufficient adhesive strength due to the effect of the cationic surfactant contained therein, even when used as a fiber sizing agent, the sizing property of the fibers is not sufficient. In addition, there have been problems such as a decrease in productivity due to unraveling, fluffing, and yarn breakage in a fiber weaving process, and insufficient strength of a fiber-reinforced plastic molded using this composition.
カチオン性界面活性剤を使用しない水性エポキシ樹脂組成物として、例えば特許文献２には、ポリオキシアルキレン基とグリシジル基とを有するアクリル樹脂を含有する水性エポキシ樹脂組成物が記載されている。前記水性エポキシ樹脂組成物は、カチオン性界面活性剤を含まないため、優れた接着強さ、繊維集束性を発現するが、経時的な吸湿により耐水性が低下することにより、この組成物を用いて成形された繊維強化プラスチックの強度低下などを引き起こすといった場合があり、集束性と耐水性に優れた集束剤が求められていた。 As an aqueous epoxy resin composition not using a cationic surfactant, for example, Patent Document 2 discloses an aqueous epoxy resin composition containing an acrylic resin having a polyoxyalkylene group and a glycidyl group. Since the aqueous epoxy resin composition does not contain a cationic surfactant, it exhibits excellent adhesive strength and fiber bundling properties. In some cases, the strength of the molded fiber-reinforced plastic is reduced, and a sizing agent excellent in sizing property and water resistance has been demanded.
本発明が解決しようとする課題は、集束性に優れ、かつ耐水性にも優れた繊維集束剤を提供することである。 The problem to be solved by the present invention is to provide a fiber sizing agent having excellent sizing properties and excellent water resistance.
本発明者は、前記課題を解決すべく検討した結果、ポリオキシアルキレン基として式（１）で表される短鎖のポリオキシアルキレン基、式（２）で表される長鎖のポリオキシアルキレン基およびグリシジル基を有する水溶性エポキシ樹脂組成物を用いた繊維集束剤が上記課題を解決できることを見出した。 The present inventors have studied to solve the above problems, and as a result, as a polyoxyalkylene group, a short-chain polyoxyalkylene group represented by the formula (1) and a long-chain polyoxyalkylene represented by the formula (2) It has been found that a fiber sizing agent using a water-soluble epoxy resin composition having a glycidyl group and a glycidyl group can solve the above problems.
すなわち本発明は、グリシジル（メタ）アクリレート（Ａ）：１０〜６０モル％、
下記一般式（１）で示されるモノマー（Ｂ）：１０〜８０モル％、及び
下記一般式（２）で示されるモノマー（Ｃ）：１０〜８０モル％を含有し、
グリシジル（メタ）アクリレート（Ａ）、モノマー（Ｂ）及びモノマー（Ｃ）の合計モル比が８０モル％以上であるモノマー混合物からなり、重量平均分子量が３０００〜１０００００である共重合体を含有する繊維集束剤である。
A monomer (B) represented by the following general formula (1): 10 to 80 mol%, and a monomer (C) represented by the following general formula (2): 10 to 80 mol%,
Fiber comprising a monomer mixture having a total molar ratio of glycidyl (meth) acrylate (A), monomer (B) and monomer (C) of 80 mol% or more, and having a weight average molecular weight of 3,000 to 100,000 It is a sizing agent.
本発明の繊維集束剤は、炭素繊維やガラス繊維などの無機繊維の集束性に優れるとともに、耐水性にも優れるので、本発明の繊維集束剤を用いて成形された繊維強化プラスチックの強度低下などが生じ難いという効果を奏する。 The fiber sizing agent of the present invention is excellent in sizing properties of inorganic fibers such as carbon fibers and glass fibers, and is also excellent in water resistance. This has the effect that hardly occurs.
以下、本発明の実施形態を説明する。
本発明の繊維集束剤は、グリシジル（メタ）アクリレート（Ａ）、上記一般式（１）で示されるモノマー（Ｂ）、及び上記一般式（２）で示されるモノマー（Ｃ）を含有するモノマー混合物からなる共重合体を含有する。
Hereinafter, embodiments of the present invention will be described.
The fiber sizing agent of the present invention is a monomer mixture containing glycidyl (meth) acrylate (A), a monomer (B) represented by the general formula (1), and a monomer (C) represented by the general formula (2). A copolymer consisting of
〔グリシジル（メタ）アクリレート（Ａ）〕
本発明で用いるグリシジル（メタ）アクリレート（Ａ）は、グリシジルアクリレート又はグリシジルメタクリレートである。工業的な入手のしやすさから、グリシジルメタクリレートを用いることが好ましい。なお、グリシジルアクリレートとグリシジルメタクリレートを併用してもよい。
[Glycidyl (meth) acrylate (A)]
The glycidyl (meth) acrylate (A) used in the present invention is glycidyl acrylate or glycidyl methacrylate. It is preferable to use glycidyl methacrylate from the viewpoint of industrial availability. In addition, you may use glycidyl acrylate and glycidyl methacrylate together.
モノマー混合物におけるグリシジル（メタ）アクリレート（Ａ）のモル比は、１０〜６０モル％であり、好ましくは１５〜５０モル％、特に好ましくは１５〜３０モル％である。グリシジル（メタ）アクリレート（Ａ）のモル比が低すぎると、集束性が低下するおそれがあり、モル比が高すぎると、共重合体の水溶性が低下するおそれがある。 The molar ratio of glycidyl (meth) acrylate (A) in the monomer mixture is 10 to 60 mol%, preferably 15 to 50 mol%, particularly preferably 15 to 30 mol%. If the molar ratio of glycidyl (meth) acrylate (A) is too low, the convergence may decrease. If the molar ratio is too high, the water solubility of the copolymer may decrease.
〔モノマー（Ｂ）〕
本発明で用いるモノマー（Ｂ）は下記一般式（１）で示される。
[Monomer (B)]
The monomer (B) used in the present invention is represented by the following general formula (1).
式中、ｍは２〜１０であり、共重合体の耐水性の観点から、３〜８が好ましく、特に好ましくは３〜５である。
Ｘ１は水素原子またはメチル基であり、重合のしやすさの観点からメチル基が好ましい。
Ｙ1は水素原子または炭素数１〜４のアルキル基である。炭素数１〜４のアルキル基としては、例えば、メチル基、エチル基、プロピル基、イソプロピル基、n-ブチル基、sec-ブチル基、イソブチル基、tert-ブチル基が挙げられ、集束剤としての耐水性と水溶性の観点からメチル基が好ましい。
Ａ1Ｏはポリオキシエチレン基またはポリオキシプロピレン基であり、共重合体の水溶性の観点からポリオキシエチレン基が好ましい。
モノマー（Ｂ）は一種類を単独で用いてもよく、２種類以上を併用してもよい。
In the formula, m is 2 to 10, and from the viewpoint of water resistance of the copolymer, m is preferably 3 to 8, and particularly preferably 3 to 5.
X 1 is a hydrogen atom or a methyl group, and is preferably a methyl group from the viewpoint of easiness of polymerization.
Y 1 is a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. Examples of the alkyl group having 1 to 4 carbon atoms include a methyl group, an ethyl group, a propyl group, an isopropyl group, an n-butyl group, a sec-butyl group, an isobutyl group, and a tert-butyl group. A methyl group is preferred from the viewpoints of water resistance and water solubility.
A 1 O is a polyoxyethylene group or a polyoxypropylene group, and is preferably a polyoxyethylene group from the viewpoint of water solubility of the copolymer.
As the monomer (B), one type may be used alone, or two or more types may be used in combination.
モノマー混合物におけるモノマー（Ｂ）のモル比は、１０〜８０モル％であり、好ましくは２０〜６０モル％、特に好ましくは３０〜５０モル％である。モノマー（Ｂ）のモル比が低すぎると、耐水性が低下するおそれがあり、モル比が高すぎると、強度低下により集束性が低下するおそれがある。 The molar ratio of the monomer (B) in the monomer mixture is from 10 to 80 mol%, preferably from 20 to 60 mol%, particularly preferably from 30 to 50 mol%. If the molar ratio of the monomer (B) is too low, water resistance may decrease, and if the molar ratio is too high, convergence may decrease due to a decrease in strength.
〔モノマー（Ｃ）〕
本発明で用いるモノマー（Ｃ）は下記一般式（２）で示される。
[Monomer (C)]
The monomer (C) used in the present invention is represented by the following general formula (2).
式中、ｎは１１〜９０であり、共重合体の耐水性の観点から、１５〜３０が好ましく、特に好ましくは２０〜２５である。
Ｘ２は水素原子またはメチル基であり、重合のしやすさの観点からメチル基が好ましい。
Ｙ２は水素原子または炭素数１〜４のアルキル基である。炭素数１〜４のアルキル基としては、例えば、メチル基、エチル基、プロピル基、イソプロピル基、n-ブチル基、sec-ブチル基、イソブチル基、tert-ブチル基が挙げられ、集束剤としての耐水性と水溶性の観点からメチル基が好ましい。
Ａ２Ｏはポリオキシエチレン基またはポリオキシプロピレン基であり、共重合体の水溶性の観点からポリオキシエチレン基が好ましい。
モノマー（Ｃ）は一種類を単独で用いてもよく、２種類以上を併用してもよい。
In the formula, n is 11 to 90, preferably 15 to 30, and particularly preferably 20 to 25, from the viewpoint of water resistance of the copolymer.
X 2 is a hydrogen atom or a methyl group, and is preferably a methyl group from the viewpoint of easiness of polymerization.
Y 2 is a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. Examples of the alkyl group having 1 to 4 carbon atoms include a methyl group, an ethyl group, a propyl group, an isopropyl group, an n-butyl group, a sec-butyl group, an isobutyl group, and a tert-butyl group. A methyl group is preferred from the viewpoints of water resistance and water solubility.
A 2 O is a polyoxyethylene group or a polyoxypropylene group, and is preferably a polyoxyethylene group from the viewpoint of water solubility of the copolymer.
As the monomer (C), one type may be used alone, or two or more types may be used in combination.
モノマー混合物におけるモノマー（Ｃ）のモル比は、１０〜８０モル％であり、好ましくは２０〜６０モル％、特に好ましくは３０〜５０モル％である。モノマー（Ｃ）のモル比が低すぎると、共重合体の水溶性が低下し、水性媒体への溶解時に析出するおそれがあり、モル比が高すぎると、耐水性や集束性が低下するおそれがある。 The molar ratio of the monomer (C) in the monomer mixture is from 10 to 80 mol%, preferably from 20 to 60 mol%, particularly preferably from 30 to 50 mol%. If the molar ratio of the monomer (C) is too low, the water solubility of the copolymer is reduced, and there is a possibility that the copolymer will precipitate when dissolved in an aqueous medium. There is.
モノマー混合物におけるグリシジル（メタ）アクリレート（Ａ）、モノマー（Ｂ）及びモノマー（Ｃ）の合計モル比が８０モル％以上であり、好ましくは８５モル％以上、特に好ましくは８５〜９５モル％である。 The total molar ratio of glycidyl (meth) acrylate (A), monomer (B) and monomer (C) in the monomer mixture is 80 mol% or more, preferably 85 mol% or more, particularly preferably 85 to 95 mol%. .
本発明におけるモノマー混合物は、グリシジル（メタ）アクリレート（Ａ）、モノマー（Ｂ）及びモノマー（Ｃ）とともに、その他のモノマーを含有していてもよい。その他のモノマーは、上記（Ａ）、（Ｂ）及び（Ｃ）以外のモノマーであり、例えば、スチレン、メチル（メタ）アクリレート、エチル（メタ）アクリレート、ｎ−ブチル（メタ）アクリレート、（メタ）アクリロニトリル、（メタ）アクリルアミドなどを挙げることができる。その他のモノマーは、一種類を単独で用いてもよく、２種類以上を併用してもよい。その中でも、集束性の観点からアクリロニトリルが好ましい。
モノマー混合物におけるその他のモノマーのモル比は、０〜２０モル％であり、好ましくは５〜１５モル％である。
The monomer mixture in the present invention may contain other monomers together with glycidyl (meth) acrylate (A), monomer (B) and monomer (C). The other monomer is a monomer other than the above (A), (B) and (C), for example, styrene, methyl (meth) acrylate, ethyl (meth) acrylate, n-butyl (meth) acrylate, (meth) Acrylonitrile, (meth) acrylamide and the like can be mentioned. As the other monomers, one type may be used alone, or two or more types may be used in combination. Among them, acrylonitrile is preferred from the viewpoint of convergence.
The molar ratio of the other monomers in the monomer mixture is from 0 to 20 mol%, preferably from 5 to 15 mol%.
上記のモノマー混合物からなる共重合体の重量平均分子量は、ポリスチレン換算で、３０００〜１０００００であり、好ましくは５０００〜８００００、特に好ましくは８０００〜５００００である。重量平均分子量が低すぎると、耐水性の低下や強度低下による集束性の低下のおそれがあり、重量平均分子量が高すぎると、水溶性が低下するおそれがある。
なお、共重合体の重量平均分子量は、例えば、ゲルパーミエーションクロマトグラフィー（ＧＰＣ）を用いて測定することができる。
The weight average molecular weight of the copolymer comprising the above monomer mixture is from 3,000 to 100,000, preferably from 5,000 to 80,000, particularly preferably from 8,000 to 50,000, in terms of polystyrene. If the weight average molecular weight is too low, convergence may decrease due to a decrease in water resistance or strength, and if the weight average molecular weight is too high, water solubility may decrease.
The weight average molecular weight of the copolymer can be measured using, for example, gel permeation chromatography (GPC).
〔共重合体の製造方法〕
次に、本発明の繊維集束剤に含有される共重合体を製造する方法について説明する。
本発明における共重合体は、グリシジル（メタ）アクリレート（Ａ）、モノマー（Ｂ）、及びモノマー（Ｃ）を少なくとも含有するモノマー混合物をラジカル重合させることにより得ることができる。重合は公知の方法で行うことができる。例えば、溶液重合、懸濁重合、乳化重合などが挙げられるが、共重合体の重量平均分子量を上記範囲内に調整しやすいという面で、溶液重合が好ましい。
(Production method of copolymer)
Next, a method for producing the copolymer contained in the fiber sizing agent of the present invention will be described.
The copolymer in the present invention can be obtained by radical polymerization of a monomer mixture containing at least glycidyl (meth) acrylate (A), monomer (B), and monomer (C). The polymerization can be performed by a known method. For example, solution polymerization, suspension polymerization, emulsion polymerization and the like can be mentioned, but solution polymerization is preferable in that the weight average molecular weight of the copolymer is easily adjusted within the above range.
重合開始剤は、公知のものを使用することができる。例えば、ジ（４−ｔ−ブチルシクロヘキシル）パーオキシジカーボネート、１，１，３，３−テトラメチルブチルパーオキシ−２−エチルヘキサノエートなどの有機過酸化物、２，２’−アゾビスイソブチロニトリルなどのアゾ系重合開始剤などを挙げることができる。これらの重合開始剤は１種類のみを用いてもよく、２種以上を併用してもよい。
重合開始剤の使用量は、用いるモノマーの組み合わせや、反応条件などに応じて適宜設定することができる。
なお、重合開始剤を投入するに際しては、例えば、全量を一括仕込みしてもよいし、一部を一括仕込みして残りを滴下してもよく、あるいは全量を滴下してもよい。また、前記モノマーとともに重合開始剤を滴下すると、反応の制御が容易となるので好ましく、さらにモノマー滴下後も重合開始剤を添加すると、残存モノマーを低減できるので好ましい。
Known polymerization initiators can be used. For example, organic peroxides such as di (4-t-butylcyclohexyl) peroxydicarbonate, 1,1,3,3-tetramethylbutylperoxy-2-ethylhexanoate, and 2,2′-azobis An azo-based polymerization initiator such as isobutyronitrile can be used. One of these polymerization initiators may be used alone, or two or more thereof may be used in combination.
The amount of the polymerization initiator to be used can be appropriately set according to the combination of the monomers used, the reaction conditions, and the like.
When the polymerization initiator is charged, for example, the whole amount may be charged at once, a part of the polymerization initiator may be charged at once, and the rest may be dropped, or the whole amount may be dropped. It is preferable to add a polymerization initiator together with the above-mentioned monomer because the control of the reaction is facilitated, and it is preferable to add the polymerization initiator even after the addition of the monomer, because the remaining monomer can be reduced.
溶液重合の際に使用する重合溶媒としては、モノマーと重合開始剤が溶解するものを使用することができ、具体的には、メタノール、エタノール、１−プロパノール、アセトン、メチルエチルケトン、プロピレングリコールモノメチルエーテルなどを挙げることができる。
重合溶媒に対するモノマー混合物の濃度は、１０〜６０質量％が好ましく、特に好ましくは２０〜５０質量％である。モノマー混合物の濃度が低すぎると、モノマーが残存しやすく、得られる共重合体の分子量が低下するおそれがあり、モノマー混合物の濃度が高すぎると、発熱を制御し難くなるおそれがある。
As the polymerization solvent used in the solution polymerization, a solvent in which the monomer and the polymerization initiator can be dissolved can be used. Specifically, methanol, ethanol, 1-propanol, acetone, methyl ethyl ketone, propylene glycol monomethyl ether, and the like can be used. Can be mentioned.
The concentration of the monomer mixture with respect to the polymerization solvent is preferably from 10 to 60% by mass, particularly preferably from 20 to 50% by mass. If the concentration of the monomer mixture is too low, the monomer tends to remain, and the molecular weight of the obtained copolymer may decrease. If the concentration of the monomer mixture is too high, it may be difficult to control heat generation.
モノマーを投入するに際しては、例えば、全量を一括仕込みしても良いし、一部を一括仕込みして残りを滴下しても良いし、あるいは全量を滴下しても良い。発熱の制御しやすさから、一部を一括仕込みして残りを滴下するか、または全量を滴下するのが好ましい。
重合温度は、重合溶媒の種類などに依存し、例えば、５０℃〜１１０℃である。重合時間は、重合開始剤の種類と重合温度に依存し、例えば、重合開始剤としてジ（４−ｔ−ブチルシクロヘキシル）パーオキシジカーボネートを使用した場合、重合温度を７０℃として重合すると、重合時間は６時間程度が適している。
以上の重合反応を行なうことにより、本発明の繊維集束剤に係る共重合体が得られる。得られた共重合体は、そのまま繊維集束剤の調製に用いてもよいし、重合反応後の反応液に、ろ取や精製を施して単離してもよい。
When charging the monomer, for example, the entire amount may be charged at once, a part of the monomer may be charged at once, and the rest may be dropped, or the entire amount may be dropped. From the viewpoint of easy control of heat generation, it is preferable to charge a part of the batch and drop the rest, or to drop the whole amount.
The polymerization temperature depends on the type of the polymerization solvent and the like, and is, for example, 50C to 110C. The polymerization time depends on the type of polymerization initiator and the polymerization temperature. For example, when di (4-t-butylcyclohexyl) peroxydicarbonate is used as the polymerization initiator, when the polymerization temperature is set to 70 ° C., the polymerization is performed. A suitable time is about 6 hours.
By performing the above polymerization reaction, a copolymer relating to the fiber sizing agent of the present invention can be obtained. The obtained copolymer may be used as it is for preparing a fiber sizing agent, or may be isolated by filtering or purifying the reaction solution after the polymerization reaction.
〔繊維集束剤〕
本発明における繊維集束剤は、好ましくは上記共重合体を水性媒体により希釈することで得られる。
希釈に用いられる水性媒体としては、例えば、水、水と混和する有機溶剤、及びこれらの混合物が挙げられる。水と混和する有機溶剤としては、例えば、メタノール、エタノール、ｎ−及びイソプロパノール等のアルコール類；アセトン、メチルエチルケトン等のケトン類；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等のポリアルキレングリコール類；Ｎ−メチルピロリドン等のラクタム類；γ−ブチロラクトン等のラクトン類；等が挙げられる。本発明では、水のみを用いても良く、また水及び水と混和する有機溶剤との混合物を用いても良く、水と混和する有機溶剤のみを用いても良い。安全性や環境に対する負荷の点から、水のみ、又は、水及び水と混和する有機溶剤との混合物が好ましく、水のみが特に好ましい。
(Fiber sizing agent)
The fiber sizing agent in the present invention is preferably obtained by diluting the above copolymer with an aqueous medium.
Examples of the aqueous medium used for dilution include water, an organic solvent miscible with water, and a mixture thereof. Examples of the water-miscible organic solvent include alcohols such as methanol, ethanol, n- and isopropanol; ketones such as acetone and methyl ethyl ketone; polyalkylene glycols such as ethylene glycol, diethylene glycol and propylene glycol; N-methylpyrrolidone And the like; lactones such as γ-butyrolactone; and the like. In the present invention, only water may be used, a mixture of water and an organic solvent miscible with water, or only an organic solvent miscible with water may be used. From the viewpoint of safety and environmental load, water alone or a mixture of water and an organic solvent miscible with water is preferred, and water alone is particularly preferred.
本発明の繊維集束剤は、良好な塗工作業性等を付与する観点から、前記繊維集束剤の全量に対して前記共重合体を５〜９０質量％の範囲で含有するものを使用することが好ましく、１０〜５０質量％の範囲で含有するものを使用することが特に好ましい。
また、本発明の繊維集束剤は、良好な塗工作業性等を付与する観点から、前記繊維集束剤の全量に対して前記水性媒体を１０〜９５質量％の範囲で含有するものを使用することが好ましく、５０〜９０質量％の範囲で含有するものを使用することが特に好ましい。
本発明の繊維集束剤は、必要に応じて、添加剤を含有していてもよい。添加剤としては、例えば、分散剤、消泡剤、防錆剤、造膜助剤、粘度調整剤、表面調整剤、可塑剤、紫外線吸収剤、酸化防止剤などが挙げられる。
The fiber sizing agent of the present invention uses, from the viewpoint of imparting good coating workability and the like, one containing the copolymer in a range of 5 to 90% by mass based on the total amount of the fiber sizing agent. It is particularly preferable to use one containing 10 to 50% by mass.
In addition, the fiber sizing agent of the present invention uses the aqueous medium in the range of 10 to 95% by mass based on the total amount of the fiber sizing agent from the viewpoint of imparting good coating workability and the like. It is particularly preferable to use one containing 50 to 90% by mass.
The fiber sizing agent of the present invention may contain an additive, if necessary. Examples of the additive include a dispersant, an antifoaming agent, a rust preventive, a film forming aid, a viscosity adjuster, a surface adjuster, a plasticizer, an ultraviolet absorber, and an antioxidant.
本発明の繊維集束剤を用いて処理可能な炭素繊維としては、一般にポリアクリロニトリル系、ピッチ系等の炭素繊維を使用することができる。なかでも、前記炭素繊維としては、優れた強度を付与する観点から、ポリアクリロニトリル系の炭素繊維を使用することが好ましい。
また、前記炭素繊維としては、より一層優れた強度等を付与する観点から、概ね０．５〜２０μｍの単糸径を有するものを使用することが好ましく、２〜１０μｍのものを使用することが特に好ましい。
As the carbon fiber that can be treated using the fiber sizing agent of the present invention, generally, a polyacrylonitrile-based or pitch-based carbon fiber can be used. Above all, it is preferable to use polyacrylonitrile-based carbon fibers from the viewpoint of imparting excellent strength.
Further, as the carbon fiber, from the viewpoint of imparting more excellent strength and the like, it is preferable to use a carbon fiber having a single yarn diameter of about 0.5 to 20 μm, preferably 2 to 10 μm. Particularly preferred.
また、本発明の繊維集束剤を用いて処理可能なガラス繊維としては、例えば、含アルカリガラス、低アルカリガラス、無アルカリガラス等を用いて形成されるガラス繊維を使用することができる。
本発明の繊維集束剤を用いて前記炭素繊維やガラス繊維を集束化し、この繊維束の表面に、本発明の繊維集束剤に含まれる共重合体からなる皮膜を形成する方法としては、例えば、本発明の繊維集束剤をキスコーター法、ローラー法、浸漬法、スプレー法、刷毛、その他公知の方法で前記繊維束の表面に均一に塗布し、次いで常温または加熱下で乾燥等することによって形成する方法が挙げられる。本発明の繊維集束剤に含まれる水性媒体は、前記塗布後に加熱ローラーや熱風、熱板等を用いて、加熱乾燥することが好ましい。
Further, as the glass fiber that can be treated using the fiber sizing agent of the present invention, for example, a glass fiber formed using alkali-containing glass, low-alkali glass, non-alkali glass, or the like can be used.
Examples of the method for forming a carbon fiber or glass fiber bundle using the fiber sizing agent of the present invention and forming a film made of a copolymer contained in the fiber sizing agent of the present invention on the surface of the fiber bundle include: The fiber sizing agent of the present invention is formed by uniformly applying the surface of the fiber bundle by a kiss coater method, a roller method, a dipping method, a spray method, a brush, or another known method, and then drying at room temperature or under heating. Method. The aqueous medium contained in the fiber sizing agent of the present invention is preferably heated and dried using a heating roller, hot air, a hot plate or the like after the application.
以下、実施例及び比較例を挙げて本発明をさらに具体的に説明する。
下記の表１及び表２に実施例および比較例に使用したモノマーの構造と略号を示す。
Hereinafter, the present invention will be described more specifically with reference to Examples and Comparative Examples.
Tables 1 and 2 below show the structures and abbreviations of the monomers used in Examples and Comparative Examples.
（合成例１）
撹拌機、温度計、冷却器、滴下ロート及び窒素導入管を取り付けた１Ｌセパラブルフラスコに、１−プロパノール２００ｇを仕込み、フラスコ内を窒素置換して、窒素雰囲気下にした。ＧＭＡ（製品名：ブレンマーＧＨ（日油（株）製））１４．６ｇ（０．１０モル）とＰＭＥ−２００（製品名：ブレンマーＰＭＥ−２００（日油（株）製））５６．８ｇ（０．２１モル）、ＰＭＥ−１０００（製品名：ブレンマーＰＭＥ−１０００（日油（株）製））２２８．７ｇ（０．２１モル）を混合したモノマー溶液、及びイソプロパノール１００ｇとジ（４−ｔ−ブチルシクロヘキシル）パーオキシジカーボネート（製品名：パーロイルＴＣＰ（日油（株）製））１０ｇを混合した重合開始剤溶液をそれぞれ調製した。
反応容器内を７０℃まで昇温し、モノマー溶液及び重合開始剤溶液を同時にそれぞれ３時間かけて滴下した。その後、７０℃で３時間反応させ共重合体Ａのイソプロパノール溶液を得た。ついで、６０℃減圧下で１８０分かけ脱溶剤したあと、イオン交換水を加え、重量平均分子量２４０００の共重合体Ａを含む繊維集束剤Ａ（固形分３０質量％）を得た。
(Synthesis example 1)
200 g of 1-propanol was charged into a 1 L separable flask equipped with a stirrer, a thermometer, a cooler, a dropping funnel, and a nitrogen inlet tube, and the inside of the flask was replaced with nitrogen to form a nitrogen atmosphere. 14.6 g (0.10 mol) of GMA (product name: Blemmer GH (manufactured by NOF Corporation)) and 56.8 g of PME-200 (product name: Blemmer PME-200 (manufactured by NOF Corporation)) 0.21 mol), a monomer solution obtained by mixing 228.7 g (0.21 mol) of PME-1000 (product name: Blemmer PME-1000 (manufactured by NOF Corporation)), 100 g of isopropanol and di (4-t A polymerization initiator solution was prepared by mixing 10 g of (-butylcyclohexyl) peroxydicarbonate (product name: Parloyl TCP (manufactured by NOF Corporation)).
The temperature inside the reaction vessel was raised to 70 ° C., and the monomer solution and the polymerization initiator solution were simultaneously added dropwise over 3 hours. Thereafter, the mixture was reacted at 70 ° C. for 3 hours to obtain an isopropanol solution of the copolymer A. Then, the solvent was removed under reduced pressure at 60 ° C. for 180 minutes, and ion-exchanged water was added to obtain a fiber sizing agent A containing a copolymer A having a weight average molecular weight of 24,000 (solid content: 30% by mass).
（合成例２）
ＧＭＡの使用量を１６．４ｇ（０．１２モル）、ＰＭＥ−２００の使用量を５５．８ｇ（０．２０モル）、ＰＭＥ−１０００の使用量を２２４．８ｇ（０．２０モル）に変更し、さらに、アクリロニトリル（製品名：アクリロニトリル（キシダ化学（株）製）３．１ｇ（０．０６モル）を混合したモノマー溶液を用いたこと以外は実施例１と同様の手法で、重量平均分子量２５０００の共重合体Ｂを含む繊維集束剤Ｂ（固形分３０質量％）を得た。
(Synthesis example 2)
The amount of GMA used was changed to 16.4 g (0.12 mole), the amount of PME-200 used was changed to 55.8 g (0.20 mole), and the amount of PME-1000 used was changed to 224.8 g (0.20 mole). Further, a weight average molecular weight was obtained in the same manner as in Example 1 except that a monomer solution containing 3.1 g (0.06 mol) of acrylonitrile (product name: acrylonitrile (manufactured by Kishida Chemical Co., Ltd.)) was used. A fiber sizing agent B (solid content: 30% by mass) containing 25,000 copolymers B was obtained.
（合成例３）
ＧＭＡの使用量を１２．８ｇ（０．０９モル）、ＰＭＥ−２００の使用量を３７．２ｇ（０．１３モル）、ＰＭＥ−１０００の使用量を２５０．０ｇ（０．２２モル）に変更したこと以外は実施例１と同様の手法で、重量平均分子量３００００の共重合体Ｃを含む繊維集束剤Ｃ（固形分３０質量％）を得た。
(Synthesis example 3)
The amount of GMA used was changed to 12.8 g (0.09 mol), the amount of PME-200 used was changed to 37.2 g (0.13 mole), and the amount of PME-1000 used was changed to 250.0 g (0.22 mole). A fiber sizing agent C containing a copolymer C having a weight-average molecular weight of 30,000 (solid content: 30% by mass) was obtained in the same manner as in Example 1 except that this was performed.
（合成例４）
ジ（４−ｔ−ブチルシクロヘキシル）パーオキシジカーボネートの使用量を１８．８ｇに変更したこと以外は実施例２と同様の手法で、重量平均分子量９０００の共重合体Ｄを含む繊維集束剤Ｄ（固形分３０質量％）を得た。
(Synthesis example 4)
A fiber sizing agent D containing a copolymer D having a weight-average molecular weight of 9,000 was prepared in the same manner as in Example 2 except that the amount of di (4-t-butylcyclohexyl) peroxydicarbonate was changed to 18.8 g. (Solid content 30% by mass) was obtained.
（合成例５）
ＧＭＡの使用量を２２．８ｇ（０．１６モル）、ＰＭＥ−２００の使用量を１４３．７ｇ（０．５２モル）、ＰＭＥ−１０００の使用量を１３３．６ｇ（０．１２モル）に変更したこと以外は実施例１と同様の手法で、重量平均分子量２００００の共重合体Ｅを含む繊維集束剤Ｅ（固形分３０重量％）を得た。
(Synthesis example 5)
The amount of GMA used was changed to 22.8 g (0.16 mole), the amount of PME-200 used was changed to 143.7 g (0.52 mole), and the amount of PME-1000 used was changed to 133.6 g (0.12 mole) A fiber sizing agent E (solid content: 30% by weight) containing a copolymer E having a weight-average molecular weight of 20,000 was obtained in the same manner as in Example 1 except that this was performed.
（合成例６）
ＧＭＡの使用量を１０．８ｇ（０．０８モル）、ＰＭＥ−２００の使用量を６３．１ｇ（０．２３モル）、ＰＭＥ−１０００の使用量を２２６．１ｇ（０．２０モル）に変更したこと以外は、実施例１と同様の手法で、重量平均分子量２８０００の共重合体Ｆを含む繊維集束剤Ｆ（固形分３０質量％）を得た。
(Synthesis example 6)
The amount of GMA used was changed to 10.8 g (0.08 mol), the amount of PME-200 used was changed to 63.1 g (0.23 mole), and the amount of PME-1000 used was changed to 226.1 g (0.20 mole). Except that, a fiber sizing agent F (solid content: 30% by mass) containing a copolymer F having a weight average molecular weight of 28,000 was obtained in the same manner as in Example 1.
（合成例７）
ＧＭＡの使用量を１０．８ｇ（０．０８モル）、ＰＭＥ−２００の使用量を１５．７ｇ（０．０６モル）、ＰＭＥ−１０００の使用量を２７３．６ｇ（０．２５モル）に変更したこと以外は実施例１と同様の手法で、重量平均分子量３００００の共重合体Ｇを含む繊維集束剤Ｇ（固形分３０質量％）を得た。
(Synthesis example 7)
The amount of GMA used was changed to 10.8 g (0.08 mol), the amount of PME-200 used was changed to 15.7 g (0.06 mol), and the amount of PME-1000 used was changed to 273.6 g (0.25 mole). A fiber sizing agent G containing a copolymer G having a weight-average molecular weight of 30,000 (solid content: 30% by mass) was obtained in the same manner as in Example 1 except that this was performed.
（合成例８）
ＧＭＡの使用量を１２．２ｇ（０．０９モル）、ＰＭＥ−１０００の使用量を２３９．３ｇ（０．１３モル）に変更し、ＰＭＥ−２００に代えてＰＰ−１０００（製品名：ブレンマーＰＰ−１０００（日油（株）製））４８．５ｇ（０．２１モル）を混合したモノマー溶液を用いたこと以外は実施例１と同様の手法で、重量平均分子量２５０００の共重合体Ｈを含む繊維集束剤Ｈ（固形分３０質量％）を得た。
(Synthesis example 8)
The amount of GMA used was changed to 12.2 g (0.09 mol) and the amount of PME-1000 used was changed to 239.3 g (0.13 mol), and PP-1000 (product name: Blemmer PP) was used instead of PME-200. A copolymer H having a weight average molecular weight of 25,000 was prepared in the same manner as in Example 1 except that a monomer solution mixed with 48.5 g (0.21 mol) of -1000 (manufactured by NOF Corporation) was used. Containing fiber sizing agent H (solid content 30% by mass) was obtained.
（合成例９）
ＧＭＡの使用量を２．６ｇ（０．０２モル）、ＰＭＥ−２００の使用量を３０．６ｇ（０．１４モル）、ＰＭＥ−１０００の使用量を２６６．８ｇ（０．２３モル）に変更したこと以外は実施例１と同様の手法で、重量平均分子量３５０００の共重合体Ｉを含む繊維集束剤Ｉ（固形分３０質量％）を得た。
(Synthesis example 9)
The amount of GMA used was changed to 2.6 g (0.02 mol), the amount of PME-200 used was changed to 30.6 g (0.14 mole), and the amount of PME-1000 used was changed to 266.8 g (0.23 mole). A fiber sizing agent I containing a copolymer I having a weight-average molecular weight of 35,000 (solid content: 30% by mass) was obtained in the same manner as in Example 1 except for the above.
（合成例１０）
ＧＭＡの使用量を４．２ｇ（０．０３モル）、ＰＭＥ−２００の量を０ｇ、ＰＭＥ−１０００の量を２９５．８ｇ（０．２７モル）に変更したこと以外は実施例１と同様の手法で、重量平均分子量２３０００の共重合体Ｊを含む繊維集束剤Ｊ（固形分３０質量％）を得た。
(Synthesis example 10)
Same as Example 1 except that the amount of GMA used was changed to 4.2 g (0.03 mol), the amount of PME-200 was changed to 0 g, and the amount of PME-1000 was changed to 295.8 g (0.27 mol). By the method, a fiber sizing agent J (solid content: 30% by mass) containing a copolymer J having a weight average molecular weight of 23,000 was obtained.
〔重量平均分子量の測定〕
ゲルパーミエーションクロマトグラフィー（ＧＰＣ）を用いて以下の条件により、共重合体Ａ〜Ｊの重量平均分子量を求めた。
装置：東ソー（株）社製、ＨＬＣ−８２２０
カラム：ｓｈｏｄｅｘ社製、ＬＦ−８０４
標準物質：ポリスチレン
溶離液：ＴＨＦ（テトラヒドロフラン）
流量：１．０ｍｌ／ｍｉｎ
カラム温度：４０℃
検出器：ＲＩ（示差屈折率検出器）
(Measurement of weight average molecular weight)
The weight average molecular weights of the copolymers A to J were determined under the following conditions using gel permeation chromatography (GPC).
Apparatus: Tosoh Corporation, HLC-8220
Column: LF-804, manufactured by Shodex
Standard substance: polystyrene Eluent: THF (tetrahydrofuran)
Flow rate: 1.0 ml / min
Column temperature: 40 ° C
Detector: RI (differential refractive index detector)
〔集束性および耐水性の評価〕
ポリアクリロニトリル系炭素繊維（直径７μｍ／１５０００本）のノーサイズ糸を束ね、前記で得た繊維集束剤Ａ〜Ｊを浸漬法で含浸させ、ローラーで絞ることで有効成分の付着量を５質量％に調整した。その後、１８０℃、６０分間加熱処理することによって、集束剤で表面処理された炭素繊維束を得た。得られた炭素繊維束を約３ｃｍの長さに切断し、試験片とした。
得られた試験片について、下記のとおり、集束性と耐水性の評価を行ない、その結果を表３及び表４に示した。なお、表３及び表４に、共重合体Ａ〜Ｊを構成する各モノマーのモル比と、共重合体Ａ〜Ｊの重量平均分子量を併せて示す。
(Evaluation of convergence and water resistance)
A bundle of polyacrylonitrile-based carbon fibers (diameter: 7 μm / 15,000) was sized, and the fiber sizing agents A to J obtained above were impregnated by a dipping method, and squeezed with a roller to reduce the amount of the attached active ingredient to 5% by mass. Was adjusted. Thereafter, a heat treatment was performed at 180 ° C. for 60 minutes to obtain a carbon fiber bundle surface-treated with a sizing agent. The obtained carbon fiber bundle was cut into a length of about 3 cm to obtain a test piece.
The obtained test pieces were evaluated for convergence and water resistance as described below, and the results are shown in Tables 3 and 4. Tables 3 and 4 also show the molar ratio of each monomer constituting the copolymers A to J and the weight average molecular weight of the copolymers A to J.
（１）集束性の評価
前記試験片１０個を抽出し、繊維のほぐれや毛羽立ちの有無を目視で確認して、繊維のほぐれや毛羽立ちの存在を確認できた試験片の個数に基づいて、下記の評価を行なった。
◎（最良）：０個
○（良）：１〜３個
△（やや不良）：４〜７個
×（不良）：８個以上
(1) Evaluation of convergence: Ten test pieces were extracted, and the presence or absence of loosening or fluffing of the fibers was visually checked. Based on the number of test pieces that could confirm the presence of loosening or fluffing of the fibers, Was evaluated.
◎ (best): 0 ○ (good): 1 to 3 △ (slightly poor): 4 to 7 （(bad): 8 or more
（２）耐水性の評価
前記試験片を２５℃でイオン交換水５０ｍＬに１時間浸漬し、浸漬前後の質量増加率を測定した。質量増加率に基づいて、下記の評価を行なった。
◎（最良）：５％未満
○（良）：５〜１０％未満
△（やや不良）：１５〜２０％未満
×（不良）：２０％以上
(2) Evaluation of Water Resistance The test piece was immersed in 50 mL of ion-exchanged water at 25 ° C. for 1 hour, and the mass increase before and after immersion was measured. The following evaluation was performed based on the mass increase rate.
◎ (best): less than 5% ○ (good): less than 5 to 10% △ (slightly poor): less than 15 to 20% × (bad): 20% or more
上記の結果より、本発明に係る実施例１〜８の繊維集束剤は、いずれも炭素繊維の集束性に優れるとともに、吸湿され難く耐水性に優れていた。
他方、比較例１では、ＧＭＡ（グリシジルメタクリレート）のモル比が低いので、集束性が不良であり、耐水性がやや不良であった。
また、比較例２では、モノマー（Ｂ）が含まれておらず、モノマー（Ｃ）のモル比が高いので、集束性がやや不良であり、耐水性が不良であった。
From the above results, all of the fiber sizing agents of Examples 1 to 8 according to the present invention were excellent in sizing properties of carbon fibers, hardly absorbed by moisture, and excellent in water resistance.
On the other hand, in Comparative Example 1, since the molar ratio of GMA (glycidyl methacrylate) was low, the convergence was poor and the water resistance was somewhat poor.
In Comparative Example 2, since the monomer (B) was not contained and the molar ratio of the monomer (C) was high, the convergence was slightly poor and the water resistance was poor.
Claims (1)
下記一般式（１）で示されるモノマー（Ｂ）：１０〜８０モル％、及び
下記一般式（２）で示されるモノマー（Ｃ）：１０〜８０モル％を含有し、
グリシジル（メタ）アクリレート（Ａ）、モノマー（Ｂ）及びモノマー（Ｃ）の合計モル比が８０モル％以上であるモノマー混合物からなり、重量平均分子量が３０００〜１０００００である共重合体を含有する繊維集束剤。
A monomer (B) represented by the following general formula (1): 10 to 80 mol%, and a monomer (C) represented by the following general formula (2): 10 to 80 mol%,
Fiber comprising a monomer mixture having a total molar ratio of glycidyl (meth) acrylate (A), monomer (B) and monomer (C) of 80 mol% or more, and having a weight average molecular weight of 3,000 to 100,000 Sizing agent.
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