JP4265205B2 - Silanol group-containing compound, production method thereof, aqueous solution of silanol group-containing compound, surface treatment agent, and glass fiber - Google Patents
Silanol group-containing compound, production method thereof, aqueous solution of silanol group-containing compound, surface treatment agent, and glass fiber Download PDFInfo
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- JP4265205B2 JP4265205B2 JP2002342070A JP2002342070A JP4265205B2 JP 4265205 B2 JP4265205 B2 JP 4265205B2 JP 2002342070 A JP2002342070 A JP 2002342070A JP 2002342070 A JP2002342070 A JP 2002342070A JP 4265205 B2 JP4265205 B2 JP 4265205B2
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- silanol group
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- 150000001875 compounds Chemical class 0.000 title claims description 199
- 125000005372 silanol group Chemical group 0.000 title claims description 159
- 239000007864 aqueous solution Substances 0.000 title claims description 143
- 239000003365 glass fiber Substances 0.000 title claims description 38
- 239000012756 surface treatment agent Substances 0.000 title claims description 29
- 238000004519 manufacturing process Methods 0.000 title claims description 26
- 238000006386 neutralization reaction Methods 0.000 claims description 32
- 125000004432 carbon atom Chemical group C* 0.000 claims description 30
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 19
- 125000003545 alkoxy group Chemical group 0.000 claims description 17
- 125000000217 alkyl group Chemical group 0.000 claims description 16
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 11
- 150000003377 silicon compounds Chemical class 0.000 claims description 10
- 125000003118 aryl group Chemical group 0.000 claims description 9
- 239000003795 chemical substances by application Substances 0.000 claims description 9
- 230000003472 neutralizing effect Effects 0.000 claims description 8
- 238000000354 decomposition reaction Methods 0.000 claims 1
- -1 silane compound Chemical class 0.000 description 86
- 229910000077 silane Inorganic materials 0.000 description 33
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 29
- 239000003960 organic solvent Substances 0.000 description 22
- 238000012360 testing method Methods 0.000 description 22
- 238000005259 measurement Methods 0.000 description 20
- 125000005395 methacrylic acid group Chemical group 0.000 description 19
- 238000006243 chemical reaction Methods 0.000 description 18
- 229920005989 resin Polymers 0.000 description 18
- 239000011347 resin Substances 0.000 description 18
- 238000006460 hydrolysis reaction Methods 0.000 description 15
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 14
- 238000006116 polymerization reaction Methods 0.000 description 14
- 238000003756 stirring Methods 0.000 description 13
- 230000000694 effects Effects 0.000 description 12
- 238000004821 distillation Methods 0.000 description 11
- 238000000034 method Methods 0.000 description 11
- 238000004381 surface treatment Methods 0.000 description 11
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 10
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 9
- 238000002360 preparation method Methods 0.000 description 8
- 239000003112 inhibitor Substances 0.000 description 7
- 239000000243 solution Substances 0.000 description 7
- 239000002131 composite material Substances 0.000 description 6
- 230000007062 hydrolysis Effects 0.000 description 6
- 229920000642 polymer Polymers 0.000 description 6
- 239000000047 product Substances 0.000 description 6
- WYTZZXDRDKSJID-UHFFFAOYSA-N (3-aminopropyl)triethoxysilane Chemical compound CCO[Si](OCC)(OCC)CCCN WYTZZXDRDKSJID-UHFFFAOYSA-N 0.000 description 5
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 5
- MXRIRQGCELJRSN-UHFFFAOYSA-N O.O.O.[Al] Chemical compound O.O.O.[Al] MXRIRQGCELJRSN-UHFFFAOYSA-N 0.000 description 5
- 125000002947 alkylene group Chemical group 0.000 description 5
- 230000015572 biosynthetic process Effects 0.000 description 5
- 238000009833 condensation Methods 0.000 description 5
- 230000005494 condensation Effects 0.000 description 5
- 230000007423 decrease Effects 0.000 description 5
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 5
- 238000003786 synthesis reaction Methods 0.000 description 5
- 229920006337 unsaturated polyester resin Polymers 0.000 description 5
- YQUVCSBJEUQKSH-UHFFFAOYSA-N 3,4-dihydroxybenzoic acid Chemical compound OC(=O)C1=CC=C(O)C(O)=C1 YQUVCSBJEUQKSH-UHFFFAOYSA-N 0.000 description 4
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 description 4
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical group [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 4
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 4
- LNTHITQWFMADLM-UHFFFAOYSA-N gallic acid Chemical compound OC(=O)C1=CC(O)=C(O)C(O)=C1 LNTHITQWFMADLM-UHFFFAOYSA-N 0.000 description 4
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 229910052710 silicon Inorganic materials 0.000 description 4
- LFMQNMXVVXHZCC-UHFFFAOYSA-N 1,3-benzothiazol-2-yl n,n-diethylcarbamodithioate Chemical compound C1=CC=C2SC(SC(=S)N(CC)CC)=NC2=C1 LFMQNMXVVXHZCC-UHFFFAOYSA-N 0.000 description 3
- 229920000536 2-Acrylamido-2-methylpropane sulfonic acid Polymers 0.000 description 3
- XHZPRMZZQOIPDS-UHFFFAOYSA-N 2-Methyl-2-[(1-oxo-2-propenyl)amino]-1-propanesulfonic acid Chemical compound OS(=O)(=O)CC(C)(C)NC(=O)C=C XHZPRMZZQOIPDS-UHFFFAOYSA-N 0.000 description 3
- 0 CO[N+](C*CC*)[O-] Chemical compound CO[N+](C*CC*)[O-] 0.000 description 3
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 3
- 239000006087 Silane Coupling Agent Substances 0.000 description 3
- 239000000654 additive Substances 0.000 description 3
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 description 3
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 description 3
- 239000012295 chemical reaction liquid Substances 0.000 description 3
- 238000004817 gas chromatography Methods 0.000 description 3
- 239000011521 glass Substances 0.000 description 3
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 3
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 125000005641 methacryl group Chemical group 0.000 description 3
- 239000000178 monomer Substances 0.000 description 3
- NWVVVBRKAWDGAB-UHFFFAOYSA-N p-methoxyphenol Chemical compound COC1=CC=C(O)C=C1 NWVVVBRKAWDGAB-UHFFFAOYSA-N 0.000 description 3
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 3
- 239000010703 silicon Substances 0.000 description 3
- 125000003396 thiol group Chemical group [H]S* 0.000 description 3
- PTBDIHRZYDMNKB-UHFFFAOYSA-N 2,2-Bis(hydroxymethyl)propionic acid Chemical compound OCC(C)(CO)C(O)=O PTBDIHRZYDMNKB-UHFFFAOYSA-N 0.000 description 2
- YCLSOMLVSHPPFV-UHFFFAOYSA-N 3-(2-carboxyethyldisulfanyl)propanoic acid Chemical compound OC(=O)CCSSCCC(O)=O YCLSOMLVSHPPFV-UHFFFAOYSA-N 0.000 description 2
- FJKROLUGYXJWQN-UHFFFAOYSA-N 4-hydroxybenzoic acid Chemical compound OC(=O)C1=CC=C(O)C=C1 FJKROLUGYXJWQN-UHFFFAOYSA-N 0.000 description 2
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 description 2
- 230000002378 acidificating effect Effects 0.000 description 2
- 238000007259 addition reaction Methods 0.000 description 2
- 239000000853 adhesive Substances 0.000 description 2
- 230000001070 adhesive 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
- 125000003277 amino group Chemical group 0.000 description 2
- 239000011668 ascorbic acid Substances 0.000 description 2
- 235000010323 ascorbic acid Nutrition 0.000 description 2
- 229960005070 ascorbic acid Drugs 0.000 description 2
- 238000005452 bending Methods 0.000 description 2
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 2
- 238000005266 casting Methods 0.000 description 2
- 239000012141 concentrate Substances 0.000 description 2
- 239000004567 concrete Substances 0.000 description 2
- 230000003247 decreasing effect Effects 0.000 description 2
- BEFDCLMNVWHSGT-UHFFFAOYSA-N ethenylcyclopentane Chemical compound C=CC1CCCC1 BEFDCLMNVWHSGT-UHFFFAOYSA-N 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 238000004880 explosion Methods 0.000 description 2
- 239000000945 filler Substances 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 230000003301 hydrolyzing effect Effects 0.000 description 2
- 239000005457 ice water Substances 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
- 239000000463 material Substances 0.000 description 2
- 239000010445 mica Substances 0.000 description 2
- 229910052618 mica group Inorganic materials 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 description 2
- 239000003973 paint Substances 0.000 description 2
- 239000002244 precipitate Substances 0.000 description 2
- 150000003141 primary amines Chemical class 0.000 description 2
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 2
- 238000010992 reflux Methods 0.000 description 2
- 235000010199 sorbic acid Nutrition 0.000 description 2
- 239000004334 sorbic acid Substances 0.000 description 2
- 229940075582 sorbic acid Drugs 0.000 description 2
- KDYFGRWQOYBRFD-UHFFFAOYSA-N succinic acid Chemical compound OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 description 2
- 239000000454 talc Substances 0.000 description 2
- 229910052623 talc Inorganic materials 0.000 description 2
- CWERGRDVMFNCDR-UHFFFAOYSA-N thioglycolic acid Chemical compound OC(=O)CS CWERGRDVMFNCDR-UHFFFAOYSA-N 0.000 description 2
- NAWXUBYGYWOOIX-SFHVURJKSA-N (2s)-2-[[4-[2-(2,4-diaminoquinazolin-6-yl)ethyl]benzoyl]amino]-4-methylidenepentanedioic acid Chemical compound C1=CC2=NC(N)=NC(N)=C2C=C1CCC1=CC=C(C(=O)N[C@@H](CC(=C)C(O)=O)C(O)=O)C=C1 NAWXUBYGYWOOIX-SFHVURJKSA-N 0.000 description 1
- GGAUUQHSCNMCAU-ZXZARUISSA-N (2s,3r)-butane-1,2,3,4-tetracarboxylic acid Chemical compound OC(=O)C[C@H](C(O)=O)[C@H](C(O)=O)CC(O)=O GGAUUQHSCNMCAU-ZXZARUISSA-N 0.000 description 1
- 125000001140 1,4-phenylene group Chemical group [H]C1=C([H])C([*:2])=C([H])C([H])=C1[*:1] 0.000 description 1
- LBEMXJWGHIEXRA-UHFFFAOYSA-N 2-[(2-carboxyphenyl)disulfanyl]benzoic acid Chemical compound OC(=O)C1=CC=CC=C1SSC1=CC=CC=C1C(O)=O LBEMXJWGHIEXRA-UHFFFAOYSA-N 0.000 description 1
- XDLMVUHYZWKMMD-UHFFFAOYSA-N 3-trimethoxysilylpropyl 2-methylprop-2-enoate Chemical compound CO[Si](OC)(OC)CCCOC(=O)C(C)=C XDLMVUHYZWKMMD-UHFFFAOYSA-N 0.000 description 1
- FEPBITJSIHRMRT-UHFFFAOYSA-N 4-hydroxybenzenesulfonic acid Chemical compound OC1=CC=C(S(O)(=O)=O)C=C1 FEPBITJSIHRMRT-UHFFFAOYSA-N 0.000 description 1
- 229940090248 4-hydroxybenzoic acid Drugs 0.000 description 1
- 239000005711 Benzoic acid Substances 0.000 description 1
- XFHJDMUEHUHAJW-UHFFFAOYSA-N CC(C)(C)NC(C=C)=O Chemical compound CC(C)(C)NC(C=C)=O XFHJDMUEHUHAJW-UHFFFAOYSA-N 0.000 description 1
- 206010008428 Chemical poisoning Diseases 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 1
- PQLVXDKIJBQVDF-UHFFFAOYSA-N acetic acid;hydrate Chemical compound O.CC(O)=O PQLVXDKIJBQVDF-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000001361 adipic acid Substances 0.000 description 1
- 235000011037 adipic acid Nutrition 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- 239000003242 anti bacterial agent Substances 0.000 description 1
- 239000002518 antifoaming agent Substances 0.000 description 1
- 239000004599 antimicrobial Substances 0.000 description 1
- 239000002216 antistatic agent Substances 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- SRSXLGNVWSONIS-UHFFFAOYSA-N benzenesulfonic acid Chemical compound OS(=O)(=O)C1=CC=CC=C1 SRSXLGNVWSONIS-UHFFFAOYSA-N 0.000 description 1
- 229940092714 benzenesulfonic acid Drugs 0.000 description 1
- 235000010233 benzoic acid Nutrition 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000006482 condensation reaction Methods 0.000 description 1
- FIRQYUPQXNPTKO-UHFFFAOYSA-N ctk0i2755 Chemical class N[SiH2]N FIRQYUPQXNPTKO-UHFFFAOYSA-N 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000010790 dilution Methods 0.000 description 1
- 239000012895 dilution Substances 0.000 description 1
- 239000000539 dimer Substances 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 239000007789 gas Substances 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
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 239000000314 lubricant Substances 0.000 description 1
- 239000004570 mortar (masonry) Substances 0.000 description 1
- PHQOGHDTIVQXHL-UHFFFAOYSA-N n'-(3-trimethoxysilylpropyl)ethane-1,2-diamine Chemical compound CO[Si](OC)(OC)CCCNCCN PHQOGHDTIVQXHL-UHFFFAOYSA-N 0.000 description 1
- MQWFLKHKWJMCEN-UHFFFAOYSA-N n'-[3-[dimethoxy(methyl)silyl]propyl]ethane-1,2-diamine Chemical compound CO[Si](C)(OC)CCCNCCN MQWFLKHKWJMCEN-UHFFFAOYSA-N 0.000 description 1
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000001971 neopentyl group Chemical group [H]C([*])([H])C(C([H])([H])[H])(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- GEVPUGOOGXGPIO-UHFFFAOYSA-N oxalic acid;dihydrate Chemical compound O.O.OC(=O)C(O)=O GEVPUGOOGXGPIO-UHFFFAOYSA-N 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- 125000001147 pentyl group Chemical group C(CCCC)* 0.000 description 1
- 125000000843 phenylene group Chemical group C1(=C(C=CC=C1)*)* 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- IUGYQRQAERSCNH-UHFFFAOYSA-N pivalic acid Chemical compound CC(C)(C)C(O)=O IUGYQRQAERSCNH-UHFFFAOYSA-N 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 125000002914 sec-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 150000004756 silanes Chemical class 0.000 description 1
- SCPYDCQAZCOKTP-UHFFFAOYSA-N silanol Chemical compound [SiH3]O SCPYDCQAZCOKTP-UHFFFAOYSA-N 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000001384 succinic acid Substances 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 150000000000 tetracarboxylic acids Chemical class 0.000 description 1
- 125000000101 thioether group Chemical group 0.000 description 1
- NJRXVEJTAYWCQJ-UHFFFAOYSA-N thiomalic acid Chemical compound OC(=O)CC(S)C(O)=O NJRXVEJTAYWCQJ-UHFFFAOYSA-N 0.000 description 1
- 125000005425 toluyl group Chemical group 0.000 description 1
- 239000013638 trimer Substances 0.000 description 1
- 229920001567 vinyl ester resin Polymers 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
- 238000004065 wastewater treatment Methods 0.000 description 1
- 125000005023 xylyl group Chemical group 0.000 description 1
Images
Description
【０００１】
【発明の属する技術分野】
本発明は、シラノール基含有化合物とその製造方法、シラノール基含有化合物の水溶液、シラノール基含有化合物を含有する表面処理剤、さらに該表面処理剤で表面処理されたガラス繊維に関する。
【０００２】
【従来の技術】
加水分解性シラン化合物は、各種基材の表面処理剤（シランカップリング剤など）として広く使用されており、通常その使用時には、それらが有する加水分解性基は予め加水分解される。
一般に、加水分解性シラン化合物を加水分解すると、ケイ素原子に結合している加水分解性基に由来する揮発性有機成分が発生する。従って、加水分解後の加水分解性シラン化合物含有液は揮発性有機成分を多量に含有することから、その取り扱い時には、有機溶剤中毒、引火、爆発等の危険性があるばかりでなく、該揮発性有機成分が大気中に揮散して環境に負荷を与える可能性が高い。
【０００３】
従って、該加水分解性シラン化合物含有液の取り扱いにあたっては、作業者の健康を守り爆発等の災害を防ぐための教育を実施せねばならないし、取り扱うための特別な設備を必要とする。さらにまた、該取り扱いに伴って発生する廃水中にも揮発性有機成分が含まれるので、これを処理するために大がかりな廃水処理設備を必要とする。
【０００４】
そこで、加水分解性シラン化合物を予め水と反応させて加水分解させ、発生する揮発性有機成分を除去する方法が考えられた。例えば、メタクリル基含有アルコキシシランを理論加水分解量よりも少ない量の水を用いて加水分解し、発生するアルコールを除去した縮合物が開示されている（特許文献１参照。）。
しかしながら、前述のメタクリル基含有アルコキシシランは、完全に加水分解しようとすると、該メタクリル基含有アルコキシシラン水溶液の粘度が高くなる。さらに場合によっては固化することもあるため、完全に加水分解された安定な水溶液を得ることは困難であった。
一方、該水溶液を酸性状態にすると、高粘度化もしくは固化させることなく該メタクリル基含有アルコキシシランを完全に加水分解することも可能である。しかし、該水溶液中における完全加水分解後のメタクリル基含有アルコキシシラン同士の縮合により、該水溶液の安定性が低下し、経時変化とともに白濁していた。すなわち、長時間安定した状態で保存することが困難であった。
【特許文献１】
特開２０００−５３６８３号公報
【０００５】
【本発明が解決しようとする課題】
そこで本発明の課題は、水溶液の状態で長期間保存した場合であっても、シラノール基含有化合物同士の縮合が一定割合以上進行することなく安定な状態を保持し得るシラノール基含有化合物を提供することである。また、中和反応によって得られる化合物の水溶液を酸性にすることなく、該中和反応によって得られる化合物を完全に加水分解することが可能なシラノール基含有化合物の製造方法を提供することである。さらには、該化合物の水溶液を提供することである。また、該化合物または該水溶液を含有する表面処理剤および該水溶液該表面処理剤で表面処理されたガラス繊維を提供することである。
【０００６】
【課題を解決するための手段】
本発明者らは前述の従来技術の課題に鑑み鋭意研究を重ねた。その結果、下記一般式（１）で表されるシラノール基含有化合物であれば、水溶液の状態で長期間保存した場合であっても、シラノール基含有化合物同士の縮合が一定割合以上進行することなく安定な状態を保持し得ること、さらに、下記一般式（４）で表されるアルコキシ基含有ケイ素化合物を、下記一般式（３）で表される化合物で中和した後、該中和反応によって得られる化合物のアルコキシルを加水分解するシラノール基含有化合物の製造方法であれば、該中和反応によって得られる化合物の水溶液を酸性にすることなく、該中和反応によって得られる化合物を完全に加水分解することが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。
【０００７】
本発明は以下の構成を有する。
（１）一般式（１）で表されるシラノール基含有化合物。
【０００８】
（２）一般式（２）で表されるシラノール基含有化合物を、一般式（３）で表される化合物で中和することを特徴とする前記第１項記載の一般式（１）で表されるシラノール基含有化合物の製造方法。
【０００９】
（３）一般式（４）で表されるアルコキシ基含有ケイ素化合物を、前記第２項記載の一般式（３）で表される化合物で中和した後、該中和反応によって得られる化合物のアルコキシル基を加水分解し、副生するアルコールを除去することを特徴とする前記第１項記載の一般式（１）で表されるシラノール基含有化合物の製造方法。
【００１０】
（４）前記第１項記載のシラノール基含有化合物の水溶液。
【００１１】
（５）水溶液に対するシラノール基含有化合物の含有割合が、０．１重量％〜７０重量％の範囲である前記第４項記載の水溶液。
【００１２】
（６）水溶液に対するアルコール成分の含有割合が４重量％未満である前記第４項または第５項記載の水溶液。
【００１３】
（７）前記第１項記載のシラノール基含有化合物を含有する表面処理剤。
【００１４】
（８）前記第４項〜第６項の何れか１項記載の水溶液を含有する表面処理剤。
【００１５】
（９）前記第７項または第８項記載の表面処理剤で表面処理されたガラス繊維。
【００１６】
（１０）一般式（５）で表されるシラノール基含有化合物。
【００１７】
（１１）前記第２項記載の一般式（２）で表されるシラノール基含有化合物を、２−アクリルアミド−２−メチルプロパンスルホン酸（下記の構造を有する化合物）で中和することを特徴とする前記第１０項記載の一般式（５）で表されるシラノール基含有化合物の製造方法。
【発明の実施の形態】
以下本発明を詳細に説明する。
本発明は一般式（１）で表されるシラノール基含有化合物である。
Ｒ2は炭素数１〜８の直鎖もしくは分岐のアルキル、または炭素数６〜１０の芳香族基である。炭素数１〜８の直鎖もしくは分岐のアルキルとしては、メチル、エチル、ｎ−プロピル、ｉ−プロピル、ｎ−ブチル、ｉ−ブチル、ｓ−ブチル、ｔ−ブチル、ペンチル、ネオペンチル、ヘキシル、ヘプチル、オクチルなどが挙げられる。炭素数６〜１０の芳香族基としては、フェニル、トルイル、キシリル、エチルフェニル、カルボキシフェニルなどを挙げることができる。Ｒ2は炭素数１〜８の直鎖もしくは分岐のアルキルが好ましい。これらのうち、メチル、エチル、ｎ−プロピルおよびｉ−プロピルが特に好ましい。
ｐは１〜６の整数であるが、２〜４の整数であることが好ましい。
ｍは０＜ｍ≦３の範囲の値である。但し、ここでいうｍとは平均組成としての値を示すものである。本発明の一般式（１）で表されるシラノール基含有化合物が単量体として存在する場合には、ｍは（３−ｎ）の値をとり、整数となる。しかし、２量体、３量体等の多量体として存在する場合には、ｍは０＜ｍ＜３の範囲の値となる。本発明の一般式（１）で表されるシラノール基含有化合物は単量体または多量体として存在することは勿論、単量体と多量体との混合物としても存在する。また、縮合反応と加水分解反応が協奏的に起こるため、ｍは常に一定の整数値をとるわけではない。なお、ｍの値は一般式（１）で表されるシラノール基含有化合物の水溶液中の濃度により平均組成としてある一定値にあり、濃度が高くなるとｍは小さくなり、濃度が低くなるとｍは大きくなる。
ｎは０または１であるが、好ましくｎは０である。なお、ｍが３の場合には、ｎは常に０である。
【００１９】
一般式（１）で表されるシラノール基含有化合物の製造方法は特に限定されるものではない。例えば、一般式（２）で表されるシラノール基含有化合物を、一般式（３）で表される化合物で中和する方法を挙げることができる。また、一般式（４）で表されるアルコキシ基含有ケイ素化合物を、一般式（３）で表される化合物で中和した後、該中和反応によって得られる化合物のアルコキシル基を加水分解し、副生するアルコールを除去する方法を挙げることもできる。
【００２０】
一般式（１）で表されるシラノール基含有化合物の製造方法は、メタ（アクリル）基が重合を起こす可能性が低いという観点から、一般式（２）で表されるシラノール基含有化合物を、一般式（３）で表される化合物で中和する方法であることが好ましい。具体的には、一級アミンとカルボン酸との中和反応（反応式１）である。
一般式（２）で示される化合物に対する一般式（３）で示される化合物の割合（一般式（３）で示される化合物／一般式（２）で示される化合物）は、モル比で０．５〜１の範囲であることが好ましい。該割合が０．５未満であると（メタ）アクリル基の含有量が少なくなるため、（メタ）アクリル官能性シランとしての性能が発揮できなくなる場合がある。また、該割合が１を超えると、一般式（３）で示される化合物が過剰分残存し、これが揮発性有機成分となる場合がある。さらには、（メタ）アクリル官能性シランとしての性能および中和後のｐＨを考慮すると、一般式（２）で示される化合物に対する一般式（３）で示される化合物の割合は、より好ましくは０．７〜１の範囲であり、特に好ましくは０．９〜１の範囲である。
【００２２】
（反応式１）で示される中和反応時の温度は０℃〜８０℃の範囲であることが好ましく、特に０℃〜５０℃の範囲であることが好ましい。該温度が８０℃を超えると、重合性である（メタ）アクリル基の重合が起こる場合がある。さらに、一般式（３）で示される化合物がアクリル酸である場合には、アクリル基と一般式（２）で示される化合物のアミノ基との付加反応がおこる。その結果、目的物の収率および純度が低下する場合がある。
（反応式１）で示される中和反応では中和熱が発生し温度が上昇することから、反応器を水浴等で冷却することが好ましい。また、中和熱の発生を押さえるため、一般式（２）で示される化合物に一般式（３）で示される化合物を少量ずつ滴下するという方法も好ましい。
【００２３】
該中和反応中（メタ）アクリル基の重合を引き起こさないため、あらかじめ一般式（３）で示される化合物中に重合禁止剤を添加しておき、これを一般式（２）で示される化合物に加えて一般式（１）で示されるシラノール基含有化合物を合成してもよい。
このとき添加する重合禁止剤は、シラノール基含有化合物の水溶液中に均一に溶解するものであればよい。具体的には、ｐ−メトキシフェノール、アスコルビン酸、ソルビン酸などが挙げられる。重合禁止剤の添加量も（メタ）アクリル官能性シランとしての性能を阻害しない量であればよい。具体的には、一般式（１）で表されるシラノール基含有化合物に対して重量比で２０００ｐｐｍ以下であればよい。
【００２４】
一般式（２）で表されるシラノール基含有化合物は、一般式（４）で表されるアミノアルコキシシランと水とを反応させ、該反応において副生する揮発性有機成分を留去する方法により製造することができる。なお、一般式（４）で表されるアミノアルコキシシランは、一般試薬として入手することができる。
ＯＲ3が加水分解性基として作用するものであれば、Ｒ3は特に限定されるものではない。加水分解により生成する揮発性有機成分の沸点が比較的低く、反応液からの該揮発性有機成分の除去が容易であるという観点から、Ｒ3は炭素数４以下のアルキルであることが好ましい。具体的には、メチル、エチル、ｉ−プロピル、ｉ−ブチルなどを挙げることができる。特に好ましくは、メチルおよびエチルである。
【００２６】
一般式（４）で表されるアミノアルコキシシランと水との反応（加水分解反応）において、アミノアルコキシシランに対する水の割合（水（モル数）／アミノアルコキシシラン（モル数））はモル比で１．５〜１０の範囲であることが好ましい。水の割合がアミノアルコキシシラン１モルに対し１．５モル未満である場合には、該反応が充分に進行せず加水分解性基が残る場合がある。また、該割合がアミノアルコキシシラン１モルに対し１０モルを越える場合には、加水分解反応後に実施する揮発性有機成分の留去においてその効率が悪化する場合がある。
【００２７】
該加水分解反応は０℃〜１００℃の範囲内で行うことが好ましく、より好ましくは４０℃〜１００℃の範囲である。
【００２８】
該加水分解反応によって揮発性有機成分が副生するが、本発明において使用する一般式（２）で表されるシラノール基含有化合物は、該揮発性有機成分の含有割合が低いものであることが好ましい。該含有割合は、一般式（２）で表されるシラノール基含有化合物の水溶液に対して４重量％未満であることが特に好ましい。該割合が４重量％未満であれば、アルコール成分の蒸気圧を元に計算すると、米国産業専門家会議（ＡＣＧＩＨ：American Conference of Governmental Industrial Hygienists）が勧告している、常温、常圧下で大気中へ放出される揮発性有機成分量が許容濃度である１０００ｐｐｍ（０．１ＭＰａ、２５℃）以下となる。
【００２９】
該含有割合を下げる方法は特に限定されるものではないが、１００Ｐａ〜１００ＫＰａの圧力下、該揮発性有機成分を留去することが好ましい。
その際の温度は特に限定されるものではないが、０〜１００℃の範囲であることが好ましく、より好ましくは４０〜１００℃の範囲である。
【００３０】
さらに、該揮発性有機成分を留去する際には、一般式（２）で表されるシラノール基含有化合物の水溶液から留去される揮発性有機成分の重量と同じ重量の水を反応液に添加することが好ましい。これにより、該水溶液が濃縮され粘度が上昇し、蒸留効率が低下する事を防止できる。
【００３１】
さらに、本発明に使用する該水溶液は、そのケイ素含有量が１７重量％以下の範囲であることが好ましい。ケイ素の含有割合が１７重量％より多いと該水溶液の粘度が非常に高くなり流動性が低くなる傾向があり、品質を一定に保つことが困難となる。
【００３２】
また、該揮発性有機成分の留去が終了した後、該水溶液の一般式（２）で表されるシラノール基含有化合物濃度を測定し、必要に応じ、水により希釈あるいは再度蒸留による濃縮操作を行い所定の濃度に調製してもよい。
【００３３】
本発明は、一般式（４）で表されるアルコキシ基含有ケイ素化合物を、一般式（３）で表される化合物で中和した後、該中和反応によって得られる化合物のアルコキシル基を加水分解し、副生するアルコールを除去することを特徴とする一般式（１）で表されるシラノール基含有化合物の製造方法である。一般式（３）で表される化合物が中和後微量残存した場合でもアルコールとともに除去できる。
【００３４】
一般式（４）で示される化合物と、一般式（３）で示される化合物との反応は、具体的には一級アミンとカルボン酸との中和反応（反応式２）である。
一般式（４）で示される化合物に対する一般式（３）で示される化合物の割合（一般式（３）で示される化合物／一般式（４）で示される化合物）は、モル比で０．５〜１の範囲であることが好ましい。該割合が０．５未満であると（メタ）アクリル基の含有量が少なくなるため（メタ）アクリル官能性シランとしての性能が発揮できなくなる場合がある。また、該割合が１を超えると、一般式（３）で示される化合物が過剰分残存し、これを完全に除去できず揮発性有機成分となる場合がある。
【００３６】
（メタ）アクリル官能性シランとしての性能および中和後のｐＨを考慮すると、一般式（４）で示される化合物に対する一般式（３）で示される化合物の割合は、より好ましくは０．７〜１の範囲であり、特に好ましくは０．９〜１の範囲である。
【００３７】
（反応式２）で示される中和反応時の温度は８０℃以下が好ましく、特に０℃〜５０℃の範囲であることが好ましい。該温度が８０℃を超える場合には、重合性の（メタ）アクリル基の重合が起こる場合がある。さらに、一般式（３）で示される化合物がアクリル酸である場合には、アクリル基と一般式（４）で示される化合物のアミノ基との付加反応がおこり、目的物の収率および純度が低下する場合がある。
【００３８】
（反応式２）で示される中和反応では中和熱が発生し温度が上昇することから、反応器を水浴等で冷却することが好ましい。また、中和熱の発生を押さえるため、一般式（４）で示される化合物に一般式（３）で示される化合物を少量ずつ滴下するという方法も好ましい。
【００３９】
該中和反応中（メタ）アクリル基の重合を引き起こさないため、あらかじめ一般式（３）で示される化合物中に重合禁止剤を添加しておき、これを一般式（４）で示される化合物に加えてもよい。
【００４０】
このとき添加する重合禁止剤は、シラノール基含有化合物の水溶液中に均一に溶解するものであればよい。具体的には、ｐ−メトキシフェノール、アスコルビン酸、ソルビン酸などが挙げられる。重合禁止剤の添加量も（メタ）アクリル官能性シランとしての性能を阻害しない量であればよい。具体的には、一般式（１）で表されるシラノール基含有化合物に対して重量比で２０００ｐｐｍ以下であればよい。
【００４１】
該中和反応によって得られる化合物のアルコキシル基の加水分解において、該化合物に対する水の割合（水（モル数）／アミノアルコキシシラン（モル数））は、モル比で１．５〜１０の範囲であることが好ましい。水の割合が該化合物１モルに対し１．５モル未満である場合には、該反応が充分に進行せず加水分解性基が残る場合がある。また、該割合が該化合物１モルに対し１０モルを越える場合には、加水分解反応後に実施する揮発性有機成分の除去においてその効率が悪化する場合がある。
【００４２】
該加水分解反応は、４０℃〜１００℃の範囲内で行われることが好ましく、より好ましくは４０℃〜８０℃の範囲内である。
【００４３】
該加水分解反応によって副生する揮発性有機成分の除去方法は特に限定されるものではないが、留去であることが好ましい。その留去方法は特に限定されるものではないが、１００Ｐａ〜１００ＫＰａの範囲の圧力下、蒸留することが好ましい。その際の温度は４０〜１００℃の範囲であることが好ましく、より好ましくは４０〜８０℃の範囲である。
【００４４】
一般式（１）で示されるシラノール基含有化合物および一般式（３）で示される化合物は、重合性の（メタ）アクリル基を含有しているため、高温になると（メタ）アクリル基の重合が起こる場合があることから、中和反応、加水分解反応、および副生揮発性有機成分除去時の温度は８０℃以下であることが好ましい。
【００４５】
該揮発性有機成分の含有割合は、一般式（１）で表されるシラノール基含有化合物の水溶液に対して４重量％未満であることが好ましい。該割合が４重量％未満であれば、アルコール成分の蒸気圧を元に計算すると、米国産業専門家会議（ＡＣＧＩＨ：American Conference of Governmental Industrial Hygienists）が勧告している、常温、常圧下で大気中へ放出される揮発性有機成分量が許容濃度である１０００ｐｐｍ（０．１ＭＰａ、２５℃）以下となる。
【００４６】
さらに、該揮発性有機成分を留去する際には、一般式（１）で表されるシラノール基含有化合物の水溶液から留去される揮発性有機成分の重量と同じ重量の水を反応液に添加することが好ましい。これにより該水溶液が濃縮され粘度が上昇し、蒸留効率が低下する事を防止できる。
【００４７】
本発明は、一般式（１）で示されるシラノール基含有化合物の水溶液である。シラノール基含有化合物の含有割合（シラノール基含有化合物の重量／（シラノール基含有化合物の重量＋水の重量））は、特に制限されるものではないが、０．１〜７０重量％の範囲であることが好ましい。シラノール基含有化合物の含有割合が７０重量％より大きいと保存時に該水溶液の粘度が非常に高くなり流動性が低くなる傾向がある。その結果、（メタ）アクリル基の重合を引き起こす可能性が高くなり、品質を一定に保つことが困難となる。したがって、必要に応じて再濃縮するかまたは水により希釈して所定の濃度に調整するのが好ましい。
【００４８】
本発明は、一般式（１）で示されるシラノール基含有化合物、または該シラノール基含有化合物の水溶液を含有する表面処理剤である。これら化合物または水溶液を含有するものであれば、その組成や物性などは特に限定されるものではない。
【００４９】
本発明の表面処理剤は、本発明の効果を損なわない範囲であれば、一般式（１）で示される本発明のシラノール基含有化合物に加えて、顔料、消泡剤、潤滑剤、防腐剤、ｐＨ調節剤、フィルム形成剤、帯電防止剤、抗菌剤、界面活性剤、および染料などから選択される他の添加剤の１種以上を含有するものであっても良い。
【００５０】
本発明の表面処理剤に含まれる一般式（１）で示されるシラノール基含有化合物の割合は特に限定されるものではないが、表面処理剤に対して０．１〜６０重量％の範囲であることが好ましい。
【００５１】
本発明の表面処理剤の用途は特に限定されるものではないが、具体的には、ガラス繊維の表面処理、タルク、マイカ等のフィラーの表面処理、鋳物用鋳型、レジンコンクリート、樹脂の表面改質および水系塗料の添加剤などを挙げることができる。その中でも特にガラス繊維の表面処理に使用した場合には、ガラス／樹脂界面を強固に結びつけることができるため、ＦＲＰなどの複合材料の性能を向上することができる。
【００５２】
本発明は、前記表面処理剤で表面処理されたガラス繊維である。ガラス繊維を表面処理する方法は、一般的に用いられる方法が採用できる。例えば、一般式（１）で示されるシラノール基含有化合物または該シラノール基含有化合物の水溶液を含有する表面処理剤を、希釈したものに、ガラス繊維を浸漬させた後、乾燥させることにより製造することができる。また、この表面処理剤を希釈したものを吹き付けた後に乾燥させることにより製造することができる。
本発明のガラス繊維は、その製品形態に限定されない。ガラス繊維製品は多岐にわたるが、例を挙げると単繊維、チョップトストランド、ロービング、ヤーン、ガラスクロスなどが示される。
【００５３】
本発明は、一般式（５）で表されるシラノール基含有化合物である。
本発明は、一般式（３）で表される化合物に代えて一般式（６）から（１３）で表される化合物のいずれか１つを用いて、一般式（２）で表されるシラノール基含有化合物を中和することを特徴とするシラノール基含有化合物の製造方法である。
また本発明は、一般式（３）で表される化合物に代えて一般式（６）から（１３）で表される化合物のいずれか１つを用いて、一般式（４）で表されるアルコキシ基含有ケイ素化合物を中和した後、該中和反応によって得られる化合物のアルコキシル基を加水分解し、副生するアルコールを除去することを特徴とするシラノール基含有化合物の製造方法である。これらの製造方法により、得られるシラノール基含有化合物も、一般式（１）で表されるシラノール基含有化合物と同様の効果を奏する。すなわち、水溶液の状態で長期間保存した場合であっても、シラノール基含有化合物同士の縮合が一定割合以上進行することなく安定な状態を保持し得る。また、揮発性有機成分を殆ど含まず、シランカップリング剤としての効果を奏するものである。
【００５５】
一般式（６）で表される化合物は、ヒドロキシル基を２つ有するカルボン酸である。Ｒ4は炭素数１〜３の直鎖もしくは分岐のアルキルである。
一般式（７）で表される化合物は、芳香族カルボン酸である。Ｒ5はＨ、水酸基または炭素数１〜４の直鎖もしくは分岐のアルキルである。
一般式（８）で表される化合物は、ジカルボン酸である。Ａ1は、単結合、炭素数２から８のアルキレンまたは１，４−フェニレンである。
一般式（９）で表される化合物は、テトラカルボン酸である。Ａ2は、任意の２つの水素がカルボキシル基との単結合に置き換えられた炭素数４〜８のアルキレンまたは任意の４つの水素がカルボキシル基との単結合に置き換えられたベンゼン環である。
一般式（１０）で表される化合物は、メルカプト基含有カルボン酸である。
Ａ３は、炭素数２〜６のアルキレンである。
一般式（１１）で表される化合物は、メルカプト基含有ジカルボン酸である。Ａ４は、任意の１つの水素がメルカプト基との単結合に置き換えられた炭素数２〜６のアルキレンである。
一般式（１２）で表される化合物は、スルフィド基含有ジカルボン酸である。Ａ５は、炭素数２〜６のアルキレンまたはフェニレンである。
一般式（１３）で表される化合物は、スルホン酸系化合物である。
Ｒ６は、Ｈ、水酸基または炭素数１〜４の直鎖もしくは分岐のアルキルである。
【００６３】
本発明は、一般式（１４）または（１５）で表されるシラノール基含有化合物である。
なお、一般式（１５）で表されるシラノール基含有化合物においては、Ｒ４は、メチルまたはエチルであることが特に好ましい。
これらは、一般式（１）で表されるシラノール基含有化合物と同様の効果を奏する。本発明の一般式（１４）で表されるシラノール基含有化合物は、一般式（２）で表されるシラノール基含有化合物に代えて、一般式（１６）で表されるシラノール基含有化合物を用いることで、一般式（１）で表されるシラノール基含有化合物の製造方法と同様に製造することができる。
本発明の一般式（１５）で表されるシラノール基含有化合物は、一般式（２）で表されるシラノール基含有化合物に代えて、一般式（１６）で表されるシラノール基含有化合物を、一般式（３）で表される化合物に代えて、一般式（６）で表される化合物を用いることで、一般式（１）で表されるシラノール基含有化合物の製造方法と同様に製造することができる。
また、本発明の一般式（１５）で表されるシラノール基含有化合物は、一般式（４）で表されるアルコキシ基含有ケイ素化合物に代えて、一般式（１７）で表されるアルコキシ基含有ケイ素化合物を用いることで、一般式（１）で表されるシラノール基含有化合物の製造方法と同様に製造することもできる。なお、これらのジアミノ系シランの製造における反応条件や好ましい範囲等はすべて一般式（１）で表されるシラノール基含有化合物の製造方法と同じである。また、効果においても同じである。
【００６５】
【実施例】
以下、実施例により詳細に説明するが、本発明はこれらの実施例に限定されるものではない。
実験例１：シラノール基含有水溶性アミノシラン化合物水溶液の合成
内部温度測定器、攪拌装置、液体配量装置、搭頂部温度測定器を備えた蒸留塔、冷却器、および蒸留生成物受器を備えた容量２リットルのフラスコに、３−アミノプロピルトリエトキシシラン（チッソ（株）製サイラエースＳ３３０）１０００ｇを仕込み、次いで配量装置から純水５００ｇを投入し、３−アミノプロピルトリエトキシシランの加水分解を行った。ガスクロマトグラフで３−アミノプロピルトリエトキシシランのピークが消失した点を加水分解の終了とし、その後該フラスコを２ＫＰａまで減圧し、６０℃で副生したエタノール５００ｇを除去した。微量の残存エタノールを除去するためさらに蒸留を続け、さらに２５０ｇ留去し、次いで除去したエタノールと同重量の純水を後該フラスコに加えて濃度および粘度を調整した。
蒸留終了後の反応液（水溶液）はガスクロマトグラフにより分析すると、エタノール含有割合は０．１重量％以下であった。該反応液（水溶液）をアルミカップに計量し、熱風オーブン中１０５℃で３時間加熱乾固させたところ、不揮発分は５０重量％であった。ケイ素含有量は１２．７重量％であり粘度は２５℃で１５０ｍｍ2／ｓであった。
【００６６】
実験例２：シラノール基含有水溶性メタクリルシラン化合物水溶液の合成
内部温度測定器、攪拌装置、滴下ロート、および還流冷却器を備えた容量１リットルのフラスコに、実験例１で得られたシラノール基含有水溶性アミノシラン化合物の水溶液５００ｇを仕込み、また滴下ロートにメタクリル酸１９５．８ｇを仕込んだ。フラスコを氷水浴に浸して内容物を冷却し、２００回転／分で内容物を攪拌しながら、滴下ロートからメタクリル酸を１時間かけて滴下した。滴下終了後、そのまま１時間攪拌を継続した。このときの該フラスコ内温は２５〜３０℃であった。
攪拌終了後、ｐＨを測定したところ６．８であり、完全に中和されていることを確認した。また、攪拌終了後の反応液（水溶液）をバイアルビンに入れてヘッドスペース部をガスクロマトグラフにより分析したところ、メタクリル酸のピークは観測されなかった。該バイアルビン中の反応液（シラノール基含有水溶性メタクリルシラン化合物水溶液）は、１週間経過後も白濁しなかった。
この反応液（水溶液）中の不揮発分含有割合を知るために、１０５℃に加熱したオーブン中に３時間放置後の重量を測定したところ、加熱前の重量の６４重量％であった。
【００６７】
実験例３：シラノール基含有水溶性アクリルシラン化合物水溶液の合成
内部温度測定器、攪拌装置、滴下ロート、および還流冷却器を備えた容量２００ミリリットルのフラスコに、実験例１で得たシラノール基含有水溶性アミノシラン化合物の水溶液６６ｇを仕込み、また滴下ロートにアクリル酸２１．６ｇを仕込んだ。フラスコを氷水浴に浸して内容物を冷却し、２００回転／分で内容物を攪拌しながら、滴下ロートからアクリル酸を１時間かけて滴下した。滴下終了後、そのまま１時間攪拌を継続した。このときの該フラスコ内温は２５〜３０℃であった。
攪拌終了後、ｐＨを測定したところ６．８であり、完全に中和されていることを確認した。また、該水溶液をバイアルビンに入れてヘッドスペース部をガスクロマトグラフにより分析したところ、アクリル酸のピークは観測されなかった。該バイアルビン中の反応液（シラノール基含有水溶性アクリルシラン化合物水溶液）は、１週間経過後も白濁しなかった。
【００６８】
実験例４：シラノール基含有水溶性メタクリルシラン化合物水溶液による水酸化アルミニウムの表面処理
スプレーバイアルに実験例２で合成したシラノール基含有水溶性メタクリルシラン化合物水溶液０．５ｇおよび純水２ｇを入れ均一に溶解させて表面処理剤を得た。ミキサーカップに水酸化アルミニウム粉体（昭和電工（株）製ハイジライトＨ−３２０）５０ｇを秤量した。ミキサーカップ内容物を攪拌しながら、該水酸化アルミニウム粉体に該表面処理剤を噴霧した。ミキサーカップにふたをし、ミキサーにて攪拌した。攪拌後、内容物を１００℃にて２０分乾燥し、乳鉢ですりつぶすことによって表面処理された水酸化アルミニウム粉体を得た。
【００６９】
実験例５：水酸化アルミニウム／不飽和ポリエステル樹脂複合材料試験片の調製カップに不飽和ポリエステル樹脂（昭和高分子（株）製リゴラック２００４ＷＮ−２）２５ｇを入れた。これに促進剤（昭和高分子（株）製リゴラック促進剤Ｅ）０．０６２５ｇ、硬化剤（日本油脂（株）製パーメックＮ）０．１２５ｇ、実験例４にて得られたシラン処理された水酸化アルミニウム粉体３７．５ｇを攪拌しながら順次加えた。５０℃で脱泡したのち、型に樹脂を流し入れて注形し、５０℃にて３時間、８０℃にて２時間加熱し樹脂を硬化させて、幅約１５ｍｍ、厚さ約２．３ｍｍ、長さ約６９ｍｍの試験片を得た。
【００７０】
実験例６：水酸化アルミニウム／不飽和ポリエステル樹脂複合材料試験片の調製水酸化アルミニウム粉体（昭和電工（株）製ハイジライトＨ−３２０）を表面処理を行わずそのまま用い、促進剤を０．２５ｇ、硬化剤を０．５ｇ用いた他は実験例５に準じて同様の大きさの試験片を得た。
【００７１】
実験例７：材料強度試験
実験例５および実験例６にて得られた複合材料試験片の曲げ試験を行った。試験方法はＪＩＳ Ｋ ６９１１に準じた。ただし、支点間距離は２０ｍｍである。試験片が折れたときの最大荷重および正確に測定した試験片の幅および厚さから曲げ強さを求めた。結果を表１に示した。
【００７２】
【表１】
表１より、実験例５で得られた試験片の方が高い強度を示した。これは、水酸化アルミニウム粉体と不飽和ポリエステル樹脂との界面が本発明で得られたシラノール基含有化合物により強固に結びついていることを示しており、表面処理剤として有効に機能していることが示される。
【００７４】
実験例８：シラノール基含有水溶性メタクリルシラン化合物水溶液によるガラス繊維の表面処理
ビーカーに実験例２で合成したシラノール基含有水溶性メタクリルシラン化合物水溶液１０ｇおよび純水９９０ｇを入れ、マグネチックスターラーにて攪拌し均一に溶解させて表面処理剤を得た。この表面処理剤中に約３０ｃｍの長さに切断したガラス繊維(直径約１６μｍ)を３０秒間浸漬し、オーブン中で１００℃にて２０分乾燥することによって表面処理されたガラス繊維を得た。
【００７５】
実験例９：マイクロドロップレット測定用試験サンプル作成
実験例８にて得られた表面処理されたガラス繊維１本を台紙に接着剤で固定した。カップに不飽和ポリエステル樹脂（昭和高分子（株）製リゴラック２００４ＷＮ−２）２０ｇおよびメタクリル酸メチル（東京化成（株）製）５ｇを入れた。これに促進剤（昭和高分子（株）製リゴラック促進剤Ｅ）０．５ｇ、硬化剤（日本油脂（株）製パーメックＮ）１ｇを攪拌しながら順次加えた。室温にて脱泡したのち、ミクロスパーテルを用いてガラス繊維に樹脂を少量塗布することにより、ガラス繊維に樹脂の微小ドロップを付着させた。これを５０℃にて２時間、８０℃にて２時間、１００℃にて３時間加熱し樹脂を硬化させて、マイクロドロップレット測定用試験サンプルを得た。
【００７６】
実験例１０：マイクロドロップレット測定用試験サンプル作成
表面処理を行わずにガラス繊維をそのまま用いた他は実験例９に準じて同様のマイクロドロップレット測定用試験サンプルを得た。
【００７７】
実験例１１：マイクロドロップレット測定
複合材界面特性評価装置ＨＭ４１０（東栄産業（株）製）にて実験例９および実験例１０にて得られたサンプルのマイクロドロップレット測定を行った。マイクロドロップレット測定とは、ガラス繊維に付着した樹脂ドロップを固定し、ガラス繊維を引き抜くときの最大荷重を求め、これからガラス／樹脂界面の界面せん断強度を評価するものである。測定の概念を図１に示した。
得られた界面せん断強度を表２に示した。
【００７８】
【表２】
【００７９】
実験例１２：
実験例１で得られたシラノール基含有水溶性アミノシラン化合物の水溶液５００ｇを８０．０ｇに、メタクリル酸１９５．８ｇを２−アクリルアミド−２−メチルプロパンスルホン酸（下記の化合物）７５．４ｇに代え、重合禁止剤としてｐ−メトキシフェノール０．０３８ｇ加えたこと以外は実験例２に準じてシラノール基含有水溶性メタクリルシラン化合物の合成を行った。
【００８０】
実験例１３：
実験例１で得られたシラノール基含有水溶性アミノシラン化合物の水溶液５００ｇを２２．１ｇに、メタクリル酸１９５．８ｇを２，２−ジメチルプロピオン酸（下記の化合物）１３．４ｇに代えたこと以外は実験例２に準じてシラノール基含有水溶性シラン化合物の合成を行った。
【００８１】
実験例１４：
実験例１で得られたシラノール基含有水溶性アミノシラン化合物の水溶液５００ｇを２２．１ｇに、メタクリル酸１９５．８ｇを安息香酸（下記の化合物）１２．２ｇに代えたこと以外は実験例２に準じてシラノール基含有水溶性シラン化合物の合成を行った。
【００８２】
実験例１５−１：
実験例１で得られたシラノール基含有水溶性アミノシラン化合物の水溶液５００ｇを２２．１ｇに、メタクリル酸１９５．８ｇを４−ヒドロキシ安息香酸（下記の化合物）１３．８ｇに代えたこと以外は実験例２に準じてシラノール基含有水溶性シラン化合物の合成を行った。
【００８３】
実験例１５−２：
実験例１で得られたシラノール基含有水溶性アミノシラン化合物の水溶液５００ｇを２０．０ｇに、メタクリル酸１９５．８ｇを３，４−ジヒドロキシ安息香酸（下記の化合物）１４．１ｇに代えたこと以外は実験例２に準じてシラノール基含有水溶性シラン化合物の合成を行った。
【００８４】
実験例１５−３：
実験例１で得られたシラノール基含有水溶性アミノシラン化合物の水溶液５００ｇを２０．０ｇに、メタクリル酸１９５．８ｇを３，４，５−トリヒドロキシ安息香酸（下記の化合物）１７．２ｇに代えたこと以外は実験例２に準じてシラノール基含有水溶性シラン化合物の合成を行った。
【００８５】
実験例１６：
実験例１で得られたシラノール基含有水溶性アミノシラン化合物の水溶液５００ｇを１０．０ｇに、メタクリル酸１９５．８ｇをシュウ酸二水和物２．８７ｇに代えたこと以外は実験例２と同様の操作を行った。
無色透明の水溶液が得られた。該水溶液は１週間以上放置しておいても白濁しなかった。また、揮発性有機溶媒のピークは観測されなかった。
【００８６】
実験例１７：
実験例１で得られたシラノール基含有水溶性アミノシラン化合物の水溶液５００ｇを１０．０ｇに、メタクリル酸１９５．８ｇをこはく酸（下記の化合物）２．６８ｇに代えたこと以外は実験例２に準じてシラノール基含有水溶性シラン化合物の合成を行った。
【００８７】
実験例１８：
実験例１で得られたシラノール基含有水溶性アミノシラン化合物の水溶液５００ｇを１０．０ｇに、メタクリル酸１９５．８ｇをアジピン酸（下記の化合物）３．３２ｇに代えたこと以外は実験例２に準じてシラノール基含有水溶性シラン化合物の合成を行った。
【００８８】
実験例１９：
実験例１で得られたシラノール基含有水溶性アミノシラン化合物の水溶液５００ｇを１０．０ｇに、メタクリル酸１９５．８ｇをテレフタル酸（下記の化合物）３．７８ｇに代えたこと以外は実験例２に準じてシラノール基含有水溶性シラン化合物の合成を行った。
【００８９】
実験例２０：
実験例１で得られたシラノール基含有水溶性アミノシラン化合物の水溶液５００ｇを１０．０ｇに、メタクリル酸１９５．８ｇをmeso−ブタン−１，２，３，４−テトラカルボン酸（下記の化合物）２．６６ｇに代えたこと以外は実験例２に準じてシラノール基含有水溶性シラン化合物の合成を行った。
【００９０】
実験例２１：
実験例１で得られたシラノール基含有水溶性アミノシラン化合物の水溶液５００ｇを１０．０ｇに、メタクリル酸１９５．８ｇをチオグリコール酸（下記の化合物）４．１９ｇに代えたこと以外は実験例２に準じてシラノール基含有水溶性シラン化合物の合成を行った。
【００９１】
実験例２２：
実験例１で得られたシラノール基含有水溶性アミノシラン化合物の水溶液５００ｇを１０．０ｇに、メタクリル酸１９５．８ｇをチオリンゴ酸（下記の化合物）３．４１ｇに代えたこと以外は実験例２に準じてシラノール基含有水溶性シラン化合物の合成を行った。
【００９２】
実験例２３：
実験例１で得られたシラノール基含有水溶性アミノシラン化合物の水溶液５００ｇを１０．０ｇに、メタクリル酸１９５．８ｇを３，３’−ジチオジプロピオン酸（下記の化合物）４．７８ｇに代えたこと以外は実験例２に準じてシラノール基含有水溶性シラン化合物の合成を行った。
【００９３】
実験例２４：
実験例１で得られたシラノール基含有水溶性アミノシラン化合物の水溶液５００ｇを１０．０ｇに、メタクリル酸１９５．８ｇを２，２’−ジチオジ安息香酸（下記の化合物）６．９６ｇに代えたこと以外は実験例２に準じてシラノール基含有水溶性シラン化合物の合成を行った。
【００９４】
実験例２５：
実験例１で得られたシラノール基含有水溶性アミノシラン化合物の水溶液５００ｇを２０．０ｇに、メタクリル酸１９５．８ｇをベンゼンスルホン酸（下記の化合物）１４．２ｇに代えたこと以外は実験例２に準じてシラノール基含有水溶性シラン化合物の合成を行った。
【００９５】
実験例２６：
実験例１で得られたシラノール基含有水溶性アミノシラン化合物の水溶液５００ｇを２０．０ｇに、メタクリル酸１９５．８ｇを４−ヒドロキシベンゼンスルホン酸（下記の化合物）１５．６ｇに代えたこと以外は実験例２に準じてシラノール基含有水溶性シラン化合物の合成を行った。
【００９６】
実験例２７：シラノール基含有水溶性ジアミノシラン化合物水溶液の合成
容量５００ミリリットルのフラスコを用いて、３−アミノプロピルトリエトキシシラン（チッソ（株）製サイラエースＳ３３０）１０００ｇをＮ−（２−アミノエチル）−３−アミノプロピルトリメトキシシラン（チッソ（株）製サイラエースＳ３２０）２２２ｇに、純水５００ｇを８１ｇに代えたこと以外は実験例１と同様の操作を行った。
【００９７】
実験例２８：
実験例１で得られたシラノール基含有水溶性アミノシラン化合物の水溶液５００ｇを実験例２７で得られたシラノール基含有水溶性ジアミノシラン化合物の水溶液１０．０ｇに、メタクリル酸１９５．８ｇを２．８２ｇに代えたこと以外は実験例２に準じてシラノール基含有水溶性メタクリルシラン化合物の合成を行った。
黄色透明の水溶液が得られた。該水溶液は１週間以上放置しておいても白濁しなかった。また、揮発性有機溶媒のピークは観測されなかった。
【００９８】
実験例２９：
実験例１で得られたシラノール基含有水溶性アミノシラン化合物の水溶液５００ｇを実験例２７で得られたシラノール基含有水溶性ジアミノシラン化合物の水溶液１０．０ｇに、メタクリル酸１９５．８ｇを５．６４ｇに代えたこと以外は実験例２に準じてシラノール基含有水溶性メタクリルシラン化合物の合成を行った。
黄色透明の水溶液が得られた。該水溶液は１週間以上放置しておいても白濁しなかった。また、揮発性有機溶媒のピークは観測されなかった。
【００９９】
実験例３０：
実験例１で得られたシラノール基含有水溶性アミノシラン化合物の水溶液５００ｇを実験例２７で得られたシラノール基含有水溶性ジアミノシラン化合物の水溶液１０．０ｇに、メタクリル酸１９５．８ｇを２，２−ジメチロールプロピオン酸４．４ｇに代えたこと以外は実験例２に準じてシラノール基含有水溶性シラン化合物の合成を行った。
黄色透明の水溶液が得られた。該水溶液は１週間以上放置しておいても白濁しなかった。また、揮発性有機溶媒のピークは観測されなかった。
【０１００】
実験例３１：
実験例１で得られたシラノール基含有水溶性アミノシラン化合物の水溶液５００ｇを実験例２７で得られたシラノール基含有水溶性ジアミノシラン化合物の水溶液１０．０ｇに、メタクリル酸１９５．８ｇを２，２−ジメチロールプロピオン酸８．８ｇに代えたこと以外は実験例２と同様の操作を行った。
黄色透明の水溶液が得られた。該水溶液は１週間以上放置しておいても白濁しなかった。また、揮発性有機溶媒のピークは観測されなかった。
【０１０１】
実験例３２：シラノール基含有水溶性ジアミノシラン化合物水溶液の合成
容量５００ミリリットルのフラスコを用いて、３−アミノプロピルトリエトキシシラン（チッソ（株）製サイラエースＳ３３０）１０００ｇをＮ−（２−アミノエチル）−３−アミノプロピルメチルジメトキシシラン（チッソ（株）製サイラエースＳ３１０）２０６ｇに、純水５００ｇを５４ｇに代えたこと以外は実験例１と同様の操作を行った。
【０１０２】
実験例３３：
実験例１で得られたシラノール基含有水溶性アミノシラン化合物の水溶液５００ｇを実験例３２で得られたシラノール基含有水溶性ジアミノシラン化合物の水溶液１０．０ｇに、メタクリル酸１９５．８ｇを２．６９ｇに代えたこと以外は実験例２に準じてシラノール基含有水溶性メタクリルシラン化合物の合成を行った。
黄色透明の水溶液が得られた。該水溶液は１週間以上放置しておいても白濁しなかった。また、揮発性有機溶媒のピークは観測されなかった。
【０１０３】
実験例３４：
実験例１で得られたシラノール基含有水溶性アミノシラン化合物の水溶液５００ｇを実験例３２で得られたシラノール基含有水溶性ジアミノシラン化合物の水溶液１０．０ｇに、メタクリル酸１９５．８ｇを５．３８ｇに代えたこと以外は実験例２に準じてシラノール基含有水溶性メタクリルシラン化合物の合成を行った。
黄色透明の水溶液が得られた。該水溶液は１週間以上放置しておいても白濁しなかった。また、揮発性有機溶媒のピークは観測されなかった。
【０１０４】
実験例３５：マイクロドロップレット測定用試験サンプル作成
実験例８にて得られたシラン処理されたガラス繊維１本を台紙に接着剤で固定した。カップにビニルエステル樹脂（昭和高分子（株）製リポキシＲ−８０６）５０ｇを入れた。これに促進剤（昭和高分子（株）製リゴラック促進剤Ｅ）０．５ｇ、硬化剤（日本油脂（株）製パーメックＮ）１ｇを攪拌しながら順次加えた。室温にて脱泡したのち、ミクロスパーテルを用いてガラス繊維に樹脂を少量塗布することにより、ガラス繊維に樹脂の微小ドロップを付着させた。これを５０℃にて２時間、８０℃にて２時間、１２０℃にて４時間加熱し樹脂を硬化させて、マイクロドロップレット測定用試験サンプルを得た。
【０１０５】
実験例３６：シラノール基含有水溶性アクリルシラン化合物水溶液によるガラス繊維の表面処理
実験例８と同様に、ビーカーに実験例１２で合成したシラノール基含有水溶性アクリルシラン化合物水溶液３０ｇおよび純水９７０ｇを入れ、マグネチックスターラーにて攪拌し均一に溶解させて表面処理剤を得た。この表面処理剤中に約３０ｃｍの長さに切断したガラス繊維(直径約１６μｍ)を３０秒間浸漬し、オーブン中で１００℃にて２０分乾燥することによって表面処理されたガラス繊維を得た。
【０１０６】
実験例３７：マイクロドロップレット測定用試験サンプル作成
実験例８にて得られた表面処理されたガラス繊維の代わりに実験例３６にて得られたシラン処理されたガラス繊維を用いた他は、実験例３５に準じて同様のマイクロドロップレット測定用試験サンプルを得た。
【０１０７】
実験例３８：メタクリル基含有アルコキシシラン化合物水溶液によるガラス繊維の表面処理
実験例８と同様に、ビーカーに３−メタクリロキシプロピルトリメトキシシラン（チッソ（株）製Ｓ７１０）１０ｇおよびｐＨを４に調整した酢酸水９９０ｇを入れ、マグネチックスターラーにて攪拌し均一に溶解させて表面処理剤を得た。その直後この表面処理剤中に約３０ｃｍの長さに切断したガラス繊維(直径約１６μｍ)を３０秒間浸漬し、オーブン中で１００℃にて２０分乾燥することによって表面処理されたガラス繊維を得た。
【０１０８】
実験例３９：マイクロドロップレット測定用試験サンプル作成
実験例８にて得られた表面処理されたガラス繊維の代わりに実験例３８にて得られた表面処理されたガラス繊維を用いた他は、実験例３５に準じて同様のマイクロドロップレット測定用試験サンプルを得た。
【０１０９】
実験例４０：マイクロドロップレット測定用試験サンプル作成
表面処理を行わずにガラス繊維をそのまま用いた他は実験例３５に準じて同様のマイクロドロップレット測定用試験サンプルを得た。
【０１１０】
実験例４１：マイクロドロップレット測定
複合材界面特性評価装置ＨＭ４１０（東栄産業（株）製）にて実験例３５、実験例３７、実験例３９および実験例４０にて得られたサンプルのマイクロドロップレット測定を行った。測定は実施例１１と同様の方法で行った。
得られた界面せん断強度を表３に示した。
【０１１１】
【表３】
これらの実験例より、本発明のシラノール基含有化合物は、水溶液の状態で長期間保存した場合であっても、安定な状態を保持し、かつシランカップリング剤としての効果を十分持つ優れた特性を持つ化合物であることが示される。
【０１１２】
【発明の効果】
本発明のシラノール基含有化合物水溶液は、水溶液の状態で長期間保存した場合であっても、シラノール基含有化合物同士の縮合が一定割合以上進行することなく安定な状態を保持し得る。さらに、表面処理剤としての効果を十分持つ優れた特性を持つ化合物である。また、本発明の製造方法は、中和反応によって得られる化合物の水溶液を酸性にすることなく、該中和反応によって得られる化合物を完全に加水分解することが可能である。
本発明の表面処理剤は、ガラス繊維の処理、タルク、マイカ等のフィラーの表面処理、鋳物用鋳型、レジンコンクリート、樹脂の表面改質および水系塗料の添加剤などへの使用に好適である。
【図面の簡単な説明】
【図１】 マイクロドロップレット測定の概念図[0001]
BACKGROUND OF THE INVENTION
The present invention relates to a silanol group-containing compound and a production method thereof, an aqueous solution of a silanol group-containing compound, a surface treatment agent containing the silanol group-containing compound, and a glass fiber surface-treated with the surface treatment agent.
[0002]
[Prior art]
Hydrolyzable silane compounds are widely used as surface treatment agents (such as silane coupling agents) for various base materials, and usually hydrolyzable groups that they have are hydrolyzed in advance when used.
In general, when a hydrolyzable silane compound is hydrolyzed, a volatile organic component derived from a hydrolyzable group bonded to a silicon atom is generated. Therefore, since the hydrolyzable silane compound-containing liquid after hydrolysis contains a large amount of volatile organic components, there is not only danger of organic solvent poisoning, ignition and explosion during handling, but also the volatile There is a high possibility that organic components will volatilize into the atmosphere and cause a burden on the environment.
[0003]
Therefore, in handling the hydrolyzable silane compound-containing liquid, education for protecting the health of workers and preventing disasters such as explosions must be carried out, and special equipment for handling is required. Furthermore, since the volatile organic component is also contained in the wastewater generated by the handling, a large-scale wastewater treatment facility is required to treat this.
[0004]
Therefore, a method has been considered in which a hydrolyzable silane compound is preliminarily reacted with water to hydrolyze it, and the generated volatile organic components are removed. For example, a condensate obtained by hydrolyzing a methacrylic group-containing alkoxysilane with a smaller amount of water than the theoretical hydrolysis amount and removing the generated alcohol is disclosed (see Patent Document 1).
However, when the aforementioned methacrylic group-containing alkoxysilane is completely hydrolyzed, the viscosity of the methacrylic group-containing alkoxysilane aqueous solution increases. Furthermore, since it may solidify depending on the case, it is difficult to obtain a completely hydrolyzed stable aqueous solution.
On the other hand, when the aqueous solution is brought into an acidic state, the methacrylic group-containing alkoxysilane can be completely hydrolyzed without increasing the viscosity or solidifying it. However, the condensation of the methacryl group-containing alkoxysilanes after complete hydrolysis in the aqueous solution decreased the stability of the aqueous solution and became cloudy with time. That is, it was difficult to store in a stable state for a long time.
[Patent Document 1]
JP 2000-53683 A
[0005]
[Problems to be solved by the present invention]
Therefore, an object of the present invention is to provide a silanol group-containing compound that can maintain a stable state without allowing condensation between the silanol group-containing compounds to proceed over a certain ratio even when stored for a long time in an aqueous solution state. That is. Moreover, it is providing the manufacturing method of the silanol group containing compound which can fully hydrolyze the compound obtained by this neutralization reaction, without acidifying the aqueous solution of the compound obtained by neutralization reaction. Furthermore, it is to provide an aqueous solution of the compound. Moreover, it is providing the surface treatment agent containing this compound or this aqueous solution, and the glass fiber surface-treated with this aqueous solution.
[0006]
[Means for Solving the Problems]
The present inventors have intensively studied in view of the above-mentioned problems of the prior art. As a result, in the case of a silanol group-containing compound represented by the following general formula (1), the condensation between the silanol group-containing compounds does not proceed over a certain ratio even when stored for a long time in the state of an aqueous solution. A stable state can be maintained, and further, after neutralizing the alkoxy group-containing silicon compound represented by the following general formula (4) with the compound represented by the following general formula (3), If it is the manufacturing method of the silanol group containing compound which hydrolyzes the alkoxyl of the compound obtained, the compound obtained by this neutralization reaction will be completely hydrolyzed, without acidifying the aqueous solution of the compound obtained by this neutralization reaction. Based on this finding, the present invention has been completed.
[0007]
The present invention has the following configuration.
(1) A silanol group-containing compound represented by the general formula (1).
[0008]
(2) The silanol group-containing compound represented by the general formula (2) is neutralized with the compound represented by the general formula (3), which is represented by the general formula (1) described in the above item 1. A method for producing a silanol group-containing compound.
[0009]
(3) After neutralizing the alkoxy group-containing silicon compound represented by the general formula (4) with the compound represented by the general formula (3) described in the above item 2, the compound obtained by the neutralization reaction The method for producing a silanol group-containing compound represented by the general formula (1) according to the above item 1, wherein the alkoxyl group is hydrolyzed to remove the by-produced alcohol.
[0010]
(4) An aqueous solution of the silanol group-containing compound as described in item 1 above.
[0011]
(5) The aqueous solution according to the above item 4, wherein the content ratio of the silanol group-containing compound to the aqueous solution is in the range of 0.1 wt% to 70 wt%.
[0012]
(6) The aqueous solution according to item 4 or 5, wherein the content ratio of the alcohol component to the aqueous solution is less than 4% by weight.
[0013]
(7) A surface treatment agent containing the silanol group-containing compound as described in item 1 above.
[0014]
(8) A surface treatment agent containing the aqueous solution according to any one of Items 4 to 6.
[0015]
(9) Glass fiber surface-treated with the surface treatment agent according to the seventh or eighth item.
[0016]
(10) A silanol group-containing compound represented by the general formula (5).
[0017]
(11) The silanol group-containing compound represented by the general formula (2) described in the above item 2 is neutralized with 2-acrylamido-2-methylpropanesulfonic acid (compound having the following structure). The manufacturing method of the silanol group containing compound represented by General formula (5) of said 10th.
DETAILED DESCRIPTION OF THE INVENTION
The present invention will be described in detail below.
The present invention is a silanol group-containing compound represented by the general formula (1).
R 2 Is a linear or branched alkyl having 1 to 8 carbon atoms or an aromatic group having 6 to 10 carbon atoms. Examples of the linear or branched alkyl having 1 to 8 carbon atoms include methyl, ethyl, n-propyl, i-propyl, n-butyl, i-butyl, s-butyl, t-butyl, pentyl, neopentyl, hexyl, heptyl Octyl and the like. Examples of the aromatic group having 6 to 10 carbon atoms include phenyl, toluyl, xylyl, ethylphenyl, carboxyphenyl and the like. R 2 Is preferably a linear or branched alkyl having 1 to 8 carbon atoms. Of these, methyl, ethyl, n-propyl and i-propyl are particularly preferred.
Although p is an integer of 1-6, it is preferable that it is an integer of 2-4.
m is a value in the range of 0 <m ≦ 3. However, m here shows the value as an average composition. When the silanol group-containing compound represented by the general formula (1) of the present invention is present as a monomer, m takes the value of (3-n) and becomes an integer. However, when it exists as a multimer such as a dimer or a trimer, m takes a value in the range of 0 <m <3. The silanol group-containing compound represented by the general formula (1) of the present invention exists not only as a monomer or multimer, but also as a mixture of a monomer and a multimer. Further, since the condensation reaction and the hydrolysis reaction occur in concert, m does not always take a constant integer value. The value of m is a certain value as an average composition depending on the concentration of the silanol group-containing compound represented by the general formula (1) in the aqueous solution. When the concentration increases, m decreases, and when the concentration decreases, m increases. Become.
n is 0 or 1, but preferably n is 0. When m is 3, n is always 0.
[0019]
The manufacturing method of the silanol group containing compound represented by General formula (1) is not specifically limited. For example, the method of neutralizing the silanol group containing compound represented by General formula (2) with the compound represented by General formula (3) can be mentioned. Moreover, after neutralizing the alkoxy group-containing silicon compound represented by the general formula (4) with the compound represented by the general formula (3), the alkoxyl group of the compound obtained by the neutralization reaction is hydrolyzed, A method of removing by-produced alcohol can also be mentioned.
[0020]
The production method of the silanol group-containing compound represented by the general formula (1) is a silanol group-containing compound represented by the general formula (2) from the viewpoint that the meta (acryl) group is less likely to cause polymerization. A method of neutralizing with the compound represented by the general formula (3) is preferable. Specifically, it is a neutralization reaction (reaction formula 1) between a primary amine and a carboxylic acid.
The ratio of the compound represented by the general formula (3) to the compound represented by the general formula (2) (the compound represented by the general formula (3) / the compound represented by the general formula (2)) is 0.5 by molar ratio. A range of ˜1 is preferable. When the ratio is less than 0.5, the content of (meth) acrylic groups decreases, and the performance as a (meth) acryl functional silane may not be exhibited. Moreover, when this ratio exceeds 1, the compound shown by General formula (3) will remain excessively, and this may become a volatile organic component. Furthermore, considering the performance as a (meth) acryl functional silane and the pH after neutralization, the ratio of the compound represented by the general formula (3) to the compound represented by the general formula (2) is more preferably 0. The range is from 0.7 to 1, particularly preferably from 0.9 to 1.
[0022]
The temperature during the neutralization reaction represented by (Reaction Formula 1) is preferably in the range of 0 ° C to 80 ° C, and particularly preferably in the range of 0 ° C to 50 ° C. When the temperature exceeds 80 ° C., polymerization of a polymerizable (meth) acryl group may occur. Furthermore, when the compound represented by the general formula (3) is acrylic acid, an addition reaction between the acrylic group and the amino group of the compound represented by the general formula (2) occurs. As a result, the yield and purity of the target product may be reduced.
In the neutralization reaction represented by (Reaction Formula 1), heat of neutralization is generated and the temperature rises. Therefore, it is preferable to cool the reactor with a water bath or the like. Moreover, in order to suppress generation | occurrence | production of the heat of neutralization, the method of dripping little by little the compound shown by General formula (3) to the compound shown by General formula (2) is also preferable.
[0023]
In order not to cause polymerization of the (meth) acrylic group during the neutralization reaction, a polymerization inhibitor is previously added to the compound represented by the general formula (3), and this is converted into the compound represented by the general formula (2). In addition, a silanol group-containing compound represented by the general formula (1) may be synthesized.
The polymerization inhibitor added at this time should just be a thing melt | dissolved uniformly in the aqueous solution of a silanol group containing compound. Specific examples include p-methoxyphenol, ascorbic acid, sorbic acid, and the like. The addition amount of the polymerization inhibitor may be an amount that does not hinder the performance as the (meth) acryl functional silane. Specifically, the weight ratio may be 2000 ppm or less with respect to the silanol group-containing compound represented by the general formula (1).
[0024]
The silanol group-containing compound represented by the general formula (2) is obtained by reacting the aminoalkoxysilane represented by the general formula (4) with water and distilling off the volatile organic components by-produced in the reaction. Can be manufactured. In addition, the amino alkoxysilane represented by General formula (4) can be obtained as a general reagent.
OR Three R acts as a hydrolyzable group, R Three Is not particularly limited. From the viewpoint that the boiling point of the volatile organic component produced by hydrolysis is relatively low and the removal of the volatile organic component from the reaction solution is easy. Three Is preferably alkyl having 4 or less carbon atoms. Specific examples include methyl, ethyl, i-propyl, i-butyl and the like. Particularly preferred are methyl and ethyl.
[0026]
In the reaction (hydrolysis reaction) of the aminoalkoxysilane represented by the general formula (4) with water, the ratio of water to aminoalkoxysilane (water (number of moles) / aminoalkoxysilane (number of moles)) is in molar ratio. A range of 1.5 to 10 is preferable. When the ratio of water is less than 1.5 mol with respect to 1 mol of aminoalkoxysilane, the reaction may not proceed sufficiently and a hydrolyzable group may remain. Moreover, when this ratio exceeds 10 mol with respect to 1 mol of amino alkoxysilanes, the efficiency may deteriorate in distillation of the volatile organic component implemented after a hydrolysis reaction.
[0027]
The hydrolysis reaction is preferably performed within a range of 0 ° C to 100 ° C, and more preferably within a range of 40 ° C to 100 ° C.
[0028]
Although a volatile organic component is by-produced by the hydrolysis reaction, the silanol group-containing compound represented by the general formula (2) used in the present invention has a low content of the volatile organic component. preferable. The content is particularly preferably less than 4% by weight based on the aqueous solution of the silanol group-containing compound represented by the general formula (2). If the proportion is less than 4% by weight, it is calculated based on the vapor pressure of the alcohol component, which is recommended by the American Conference of Governmental Industrial Hygienists (ACGIH). The amount of volatile organic components released into the water is an allowable concentration of 1000 ppm (0.1 MPa, 25 ° C.) or less.
[0029]
The method for reducing the content ratio is not particularly limited, but it is preferable to distill off the volatile organic component under a pressure of 100 Pa to 100 KPa.
Although the temperature in that case is not specifically limited, It is preferable that it is the range of 0-100 degreeC, More preferably, it is the range of 40-100 degreeC.
[0030]
Furthermore, when distilling off the volatile organic component, water having the same weight as the weight of the volatile organic component distilled off from the aqueous solution of the silanol group-containing compound represented by the general formula (2) is used as the reaction solution. It is preferable to add. Thereby, it can prevent that this aqueous solution concentrates, a viscosity rises, and distillation efficiency falls.
[0031]
Further, the aqueous solution used in the present invention preferably has a silicon content in the range of 17% by weight or less. If the silicon content is more than 17% by weight, the viscosity of the aqueous solution tends to be very high and the fluidity tends to be low, making it difficult to keep the quality constant.
[0032]
In addition, after the distillation of the volatile organic components is completed, the concentration of the silanol group-containing compound represented by the general formula (2) of the aqueous solution is measured, and if necessary, dilution with water or concentration by distillation again is performed. And may be adjusted to a predetermined concentration.
[0033]
In the present invention, the alkoxy group-containing silicon compound represented by the general formula (4) is neutralized with the compound represented by the general formula (3), and then the alkoxyl group of the compound obtained by the neutralization reaction is hydrolyzed. And a method for producing a silanol group-containing compound represented by the general formula (1), wherein by-produced alcohol is removed. Even when a small amount of the compound represented by the general formula (3) remains after neutralization, it can be removed together with alcohol.
[0034]
The reaction between the compound represented by the general formula (4) and the compound represented by the general formula (3) is specifically a neutralization reaction (reaction formula 2) between a primary amine and a carboxylic acid.
The ratio of the compound represented by the general formula (3) to the compound represented by the general formula (4) (the compound represented by the general formula (3) / the compound represented by the general formula (4)) is 0.5 by molar ratio. A range of ˜1 is preferable. When the ratio is less than 0.5, the content of the (meth) acrylic group decreases, so that the performance as a (meth) acryl functional silane may not be exhibited. On the other hand, when the ratio exceeds 1, an excess of the compound represented by the general formula (3) remains, which may not be completely removed and may become a volatile organic component.
[0036]
Considering the performance as a (meth) acryl functional silane and the pH after neutralization, the ratio of the compound represented by the general formula (3) to the compound represented by the general formula (4) is more preferably 0.7 to 1 and particularly preferably in the range of 0.9-1.
[0037]
The temperature during the neutralization reaction represented by (Reaction Formula 2) is preferably 80 ° C. or less, and particularly preferably in the range of 0 ° C. to 50 ° C. When the temperature exceeds 80 ° C., polymerization of a polymerizable (meth) acryl group may occur. Further, when the compound represented by the general formula (3) is acrylic acid, an addition reaction between the acrylic group and the amino group of the compound represented by the general formula (4) occurs, and the yield and purity of the target product are reduced. May decrease.
[0038]
In the neutralization reaction represented by (Reaction Formula 2), heat of neutralization is generated and the temperature rises. Therefore, the reactor is preferably cooled with a water bath or the like. Moreover, in order to suppress generation | occurrence | production of the heat of neutralization, the method of dripping little by little the compound shown by General formula (3) to the compound shown by General formula (4) is also preferable.
[0039]
In order not to cause polymerization of the (meth) acrylic group during the neutralization reaction, a polymerization inhibitor is added in advance to the compound represented by the general formula (3), and this is converted into the compound represented by the general formula (4). May be added.
[0040]
The polymerization inhibitor added at this time may be any that dissolves uniformly in the aqueous solution of the silanol group-containing compound. Specific examples include p-methoxyphenol, ascorbic acid, sorbic acid, and the like. The addition amount of the polymerization inhibitor may be an amount that does not hinder the performance as the (meth) acryl functional silane. Specifically, the weight ratio may be 2000 ppm or less with respect to the silanol group-containing compound represented by the general formula (1).
[0041]
In the hydrolysis of the alkoxyl group of the compound obtained by the neutralization reaction, the ratio of water to the compound (water (number of moles) / aminoalkoxysilane (number of moles)) is in the range of 1.5 to 10 in molar ratio. Preferably there is. When the ratio of water is less than 1.5 mol with respect to 1 mol of the compound, the reaction may not proceed sufficiently and a hydrolyzable group may remain. Moreover, when this ratio exceeds 10 mol with respect to 1 mol of this compound, the efficiency may deteriorate in the removal of the volatile organic component implemented after a hydrolysis reaction.
[0042]
The hydrolysis reaction is preferably performed within a range of 40 ° C to 100 ° C, and more preferably within a range of 40 ° C to 80 ° C.
[0043]
The method for removing volatile organic components by-produced by the hydrolysis reaction is not particularly limited, but is preferably distilled off. The distillation method is not particularly limited, but distillation is preferably performed under a pressure in the range of 100 Pa to 100 KPa. The temperature at that time is preferably in the range of 40 to 100 ° C, more preferably in the range of 40 to 80 ° C.
[0044]
Since the silanol group-containing compound represented by the general formula (1) and the compound represented by the general formula (3) contain a polymerizable (meth) acrylic group, polymerization of the (meth) acrylic group occurs at a high temperature. Since it may occur, the temperature during neutralization reaction, hydrolysis reaction, and removal of by-product volatile organic components is preferably 80 ° C. or less.
[0045]
It is preferable that the content rate of this volatile organic component is less than 4 weight% with respect to the aqueous solution of the silanol group containing compound represented by General formula (1). If the proportion is less than 4% by weight, it is calculated based on the vapor pressure of the alcohol component, which is recommended by the American Conference of Governmental Industrial Hygienists (ACGIH). The amount of volatile organic components released into the water is an allowable concentration of 1000 ppm (0.1 MPa, 25 ° C.) or less.
[0046]
Furthermore, when distilling off the volatile organic component, water having the same weight as the weight of the volatile organic component distilled off from the aqueous solution of the silanol group-containing compound represented by the general formula (1) is used as the reaction solution. It is preferable to add. As a result, the aqueous solution is concentrated to increase the viscosity and prevent the distillation efficiency from decreasing.
[0047]
The present invention is an aqueous solution of a silanol group-containing compound represented by the general formula (1). The content ratio of the silanol group-containing compound (weight of silanol group-containing compound / (weight of silanol group-containing compound + weight of water)) is not particularly limited, but is in the range of 0.1 to 70% by weight. It is preferable. When the content of the silanol group-containing compound is more than 70% by weight, the viscosity of the aqueous solution tends to be very high during storage and the fluidity tends to be low. As a result, there is a high possibility of causing polymerization of (meth) acrylic groups, and it becomes difficult to keep the quality constant. Therefore, it is preferable to re-concentrate as necessary or dilute with water to adjust to a predetermined concentration.
[0048]
This invention is a surface treating agent containing the silanol group containing compound shown by General formula (1), or the aqueous solution of this silanol group containing compound. As long as these compounds or aqueous solutions are contained, the composition and physical properties thereof are not particularly limited.
[0049]
As long as the surface treatment agent of the present invention is within a range not impairing the effects of the present invention, in addition to the silanol group-containing compound of the present invention represented by the general formula (1), a pigment, an antifoaming agent, a lubricant, an antiseptic agent , One or more of other additives selected from pH adjusters, film forming agents, antistatic agents, antibacterial agents, surfactants, dyes, and the like.
[0050]
The ratio of the silanol group-containing compound represented by the general formula (1) contained in the surface treatment agent of the present invention is not particularly limited, but is in the range of 0.1 to 60% by weight with respect to the surface treatment agent. It is preferable.
[0051]
Although the use of the surface treatment agent of the present invention is not particularly limited, specifically, surface treatment of glass fiber, surface treatment of fillers such as talc and mica, casting mold, resin concrete, resin surface modification. Quality and water-based paint additives. Among them, particularly when used for the surface treatment of glass fiber, the glass / resin interface can be firmly bound, so that the performance of a composite material such as FRP can be improved.
[0052]
The present invention is a glass fiber surface-treated with the surface treatment agent. A generally used method can be adopted as a method of surface-treating the glass fiber. For example, the surface treatment agent containing the silanol group-containing compound represented by the general formula (1) or the aqueous solution of the silanol group-containing compound is manufactured by immersing glass fiber in a diluted solution and then drying it. Can do. Moreover, it can manufacture by making it dry after spraying what diluted this surface treating agent.
The glass fiber of the present invention is not limited to its product form. Glass fiber products are diverse, but examples include single fibers, chopped strands, rovings, yarns, and glass cloths.
[0053]
The present invention is a silanol group-containing compound represented by the general formula (5).
In the present invention, the silanol represented by the general formula (2) is obtained by using any one of the compounds represented by the general formulas (6) to (13) instead of the compound represented by the general formula (3). A method for producing a silanol group-containing compound comprising neutralizing a group-containing compound.
Moreover, this invention is represented by General formula (4) using any one of the compounds represented by General formula (6) to (13) instead of the compound represented by General formula (3). A method for producing a silanol group-containing compound, comprising neutralizing an alkoxy group-containing silicon compound and then hydrolyzing an alkoxyl group of the compound obtained by the neutralization reaction to remove by-produced alcohol. The silanol group-containing compound obtained by these production methods also has the same effect as the silanol group-containing compound represented by the general formula (1). That is, even when it is stored for a long time in the state of an aqueous solution, the condensation between silanol group-containing compounds can be maintained in a stable state without proceeding at a certain rate or more. Further, it contains almost no volatile organic component and exhibits an effect as a silane coupling agent.
[0055]
The compound represented by the general formula (6) is a carboxylic acid having two hydroxyl groups. R Four Is a linear or branched alkyl having 1 to 3 carbon atoms.
The compound represented by the general formula (7) is an aromatic carboxylic acid. R Five Is H, a hydroxyl group or a linear or branched alkyl having 1 to 4 carbon atoms.
The compound represented by the general formula (8) is a dicarboxylic acid. A 1 Is a single bond, alkylene having 2 to 8 carbon atoms or 1,4-phenylene.
The compound represented by the general formula (9) is tetracarboxylic acid. A 2 Is an alkylene having 4 to 8 carbon atoms in which any two hydrogens are replaced with a single bond with a carboxyl group, or a benzene ring in which any four hydrogens are replaced with a single bond with a carboxyl group.
The compound represented by the general formula (10) is a mercapto group-containing carboxylic acid.
A 3 Is alkylene having 2 to 6 carbon atoms.
The compound represented by the general formula (11) is a mercapto group-containing dicarboxylic acid. A 4 Is an alkylene having 2 to 6 carbon atoms in which any one hydrogen is replaced by a single bond with a mercapto group.
The compound represented by the general formula (12) is a sulfide group-containing dicarboxylic acid. A 5 Is alkylene or phenylene having 2 to 6 carbon atoms.
The compound represented by the general formula (13) is a sulfonic acid compound.
R 6 Is H, a hydroxyl group, or a linear or branched alkyl having 1 to 4 carbon atoms.
[0063]
The present invention is a silanol group-containing compound represented by the general formula (14) or (15).
In the silanol group-containing compound represented by the general formula (15), R 4 Is particularly preferably methyl or ethyl.
These have the same effects as the silanol group-containing compound represented by the general formula (1). The silanol group-containing compound represented by the general formula (14) of the present invention uses the silanol group-containing compound represented by the general formula (16) instead of the silanol group-containing compound represented by the general formula (2). Thus, it can be produced in the same manner as the production method of the silanol group-containing compound represented by the general formula (1).
The silanol group-containing compound represented by the general formula (15) of the present invention is a silanol group-containing compound represented by the general formula (16) instead of the silanol group-containing compound represented by the general formula (2). It manufactures similarly to the manufacturing method of the silanol group containing compound represented by General formula (1) by using the compound represented by General formula (6) instead of the compound represented by General formula (3). be able to.
Further, the silanol group-containing compound represented by the general formula (15) of the present invention contains an alkoxy group-containing compound represented by the general formula (17) instead of the alkoxy group-containing silicon compound represented by the general formula (4). By using a silicon compound, it can also be produced in the same manner as the production method of the silanol group-containing compound represented by the general formula (1). In addition, reaction conditions, preferable ranges, etc. in the production of these diamino silanes are all the same as the method for producing the silanol group-containing compound represented by the general formula (1). The effect is also the same.
[0065]
【Example】
EXAMPLES Hereinafter, although it demonstrates in detail by an Example, this invention is not limited to these Examples.
Experimental Example 1: Synthesis of aqueous solution of silanol group-containing water-soluble aminosilane compound
3-aminopropyltriethoxysilane was added to a 2-liter flask equipped with an internal temperature measuring device, a stirring device, a liquid metering device, a distillation tower equipped with a top temperature measuring device, a condenser, and a distillation product receiver. (Chizo Co., Ltd. product Sila Ace S330) 1000g was prepared, and then 500g of pure water was added from a metering device to hydrolyze 3-aminopropyltriethoxysilane. The point at which the peak of 3-aminopropyltriethoxysilane disappeared by gas chromatography was the end of hydrolysis, and then the flask was decompressed to 2 KPa to remove 500 g of ethanol by-produced at 60 ° C. Distillation was continued to remove a trace amount of residual ethanol, 250 g was further distilled off, and then pure water having the same weight as the removed ethanol was added to the flask to adjust the concentration and viscosity.
When the reaction liquid (aqueous solution) after completion of the distillation was analyzed by gas chromatography, the ethanol content was 0.1% by weight or less. The reaction solution (aqueous solution) was weighed into an aluminum cup and heated to dryness in a hot air oven at 105 ° C. for 3 hours. As a result, the nonvolatile content was 50% by weight. Silicon content is 12.7% by weight and viscosity is 150mm at 25 ° C. 2 / S.
[0066]
Experimental Example 2: Synthesis of an aqueous solution of a water-soluble methacrylsilane compound containing a silanol group
500 g of the aqueous solution of the silanol group-containing water-soluble aminosilane compound obtained in Experimental Example 1 was charged into a 1-liter flask equipped with an internal temperature measuring device, a stirrer, a dropping funnel, and a reflux condenser. 195.8 g of acid was charged. The flask was immersed in an ice water bath to cool the contents, and methacrylic acid was added dropwise from the dropping funnel over 1 hour while stirring the contents at 200 rpm. After completion of the dropping, stirring was continued for 1 hour. The temperature inside the flask at this time was 25 to 30 ° C.
After the stirring, the pH was measured and found to be 6.8, confirming complete neutralization. Moreover, when the reaction liquid (aqueous solution) after completion | finish of stirring was put into the vial bottle and the head space part was analyzed by the gas chromatograph, the peak of methacrylic acid was not observed. The reaction liquid (silanol group-containing water-soluble methacrylsilane compound aqueous solution) in the vial was not clouded even after one week.
In order to know the non-volatile content ratio in the reaction solution (aqueous solution), the weight after standing for 3 hours in an oven heated to 105 ° C. was measured and found to be 64% by weight of the weight before heating.
[0067]
Experimental Example 3: Synthesis of aqueous solution of water-soluble acrylic silane compound containing silanol group
66 g of an aqueous solution of the silanol group-containing water-soluble aminosilane compound obtained in Experimental Example 1 was charged into a 200-ml flask equipped with an internal temperature measuring device, a stirrer, a dropping funnel, and a reflux condenser, and acrylic acid was added to the dropping funnel. 21.6 g was charged. The flask was immersed in an ice-water bath to cool the contents, and acrylic acid was dropped from the dropping funnel over 1 hour while stirring the contents at 200 rpm. After completion of the dropping, stirring was continued for 1 hour. The temperature inside the flask at this time was 25 to 30 ° C.
After the stirring, the pH was measured and found to be 6.8, confirming complete neutralization. Further, when the aqueous solution was put into a vial and the headspace portion was analyzed by gas chromatography, no acrylic acid peak was observed. The reaction solution (silanol group-containing water-soluble acrylsilane compound aqueous solution) in the vial was not clouded even after 1 week.
[0068]
Experimental Example 4: Surface treatment of aluminum hydroxide with water-soluble methacrylsilane compound containing silanol group
In a spray vial, 0.5 g of the silanol group-containing water-soluble methacrylsilane compound aqueous solution synthesized in Experimental Example 2 and 2 g of pure water were added and uniformly dissolved to obtain a surface treatment agent. In a mixer cup, 50 g of aluminum hydroxide powder (Hijilite H-320 manufactured by Showa Denko KK) was weighed. The surface treatment agent was sprayed onto the aluminum hydroxide powder while stirring the contents of the mixer cup. The mixer cup was covered and stirred with a mixer. After stirring, the contents were dried at 100 ° C. for 20 minutes and ground with an mortar to obtain surface-treated aluminum hydroxide powder.
[0069]
Experimental Example 5: Preparation of Aluminum Hydroxide / Unsaturated Polyester Resin Composite Specimen 25 g of unsaturated polyester resin (Rigolac 2004 WN-2 manufactured by Showa Polymer Co., Ltd.) was placed in a cup. To this, 0.0625 g of accelerator (Showa Polymer Co., Ltd. Rigolac accelerator E), 0.125 g of curing agent (Permec N manufactured by Nippon Oil & Fats Co., Ltd.), silane-treated water obtained in Experimental Example 4 37.5 g of aluminum oxide powder was sequentially added with stirring. After defoaming at 50 ° C., the resin was poured into a mold and cast, and the resin was cured by heating at 50 ° C. for 3 hours and at 80 ° C. for 2 hours. The width was about 15 mm, the thickness was about 2.3 mm, A test piece having a length of about 69 mm was obtained.
[0070]
Experimental Example 6: Preparation of Aluminum Hydroxide / Unsaturated Polyester Resin Composite Specimen Aluminum hydroxide powder (Hijilite H-320 manufactured by Showa Denko KK) was used as it was without surface treatment. A test piece of the same size was obtained according to Experimental Example 5 except that 25 g and 0.5 g of the curing agent were used.
[0071]
Experimental Example 7: Material strength test
The composite material test pieces obtained in Experimental Example 5 and Experimental Example 6 were subjected to a bending test. The test method conformed to JIS K 6911. However, the distance between fulcrums is 20 mm. The bending strength was determined from the maximum load when the specimen was broken and the width and thickness of the specimen measured accurately. The results are shown in Table 1.
[0072]
[Table 1]
From Table 1, the test piece obtained in Experimental Example 5 showed higher strength. This indicates that the interface between the aluminum hydroxide powder and the unsaturated polyester resin is firmly bound by the silanol group-containing compound obtained in the present invention, and functions effectively as a surface treatment agent. Is shown.
[0074]
Experimental Example 8: Surface treatment of glass fiber with silanol group-containing water-soluble methacrylsilane compound aqueous solution
Into a beaker, 10 g of the silanol group-containing water-soluble methacrylsilane compound aqueous solution synthesized in Experimental Example 2 and 990 g of pure water were added and stirred uniformly with a magnetic stirrer to obtain a surface treatment agent. Glass fibers (diameter: about 16 μm) cut to a length of about 30 cm were immersed in the surface treatment agent for 30 seconds and dried in an oven at 100 ° C. for 20 minutes to obtain surface-treated glass fibers.
[0075]
Experimental Example 9: Preparation of test sample for microdroplet measurement
One surface-treated glass fiber obtained in Experimental Example 8 was fixed to the mount with an adhesive. 20 g of unsaturated polyester resin (Rigolac 2004 WN-2 manufactured by Showa High Polymer Co., Ltd.) and 5 g of methyl methacrylate (manufactured by Tokyo Chemical Industry Co., Ltd.) were placed in the cup. To this, 0.5 g of an accelerator (Rigolac accelerator E, manufactured by Showa Polymer Co., Ltd.) and 1 g of a curing agent (Permec N, manufactured by NOF Corporation) were sequentially added while stirring. After defoaming at room temperature, a small drop of resin was adhered to the glass fiber by applying a small amount of resin to the glass fiber using a micropartel. This was heated at 50 ° C. for 2 hours, 80 ° C. for 2 hours, and 100 ° C. for 3 hours to cure the resin, thereby obtaining a microdroplet measurement test sample.
[0076]
Experimental Example 10: Preparation of test sample for microdroplet measurement
A similar microdroplet measurement test sample was obtained according to Experimental Example 9 except that the glass fiber was used as it was without surface treatment.
[0077]
Experimental Example 11: Microdroplet measurement
The microdroplet measurement of the samples obtained in Experimental Example 9 and Experimental Example 10 was performed with a composite material interface property evaluation apparatus HM410 (manufactured by Toei Sangyo Co., Ltd.). In the microdroplet measurement, the resin drop adhered to the glass fiber is fixed, the maximum load when the glass fiber is pulled out is obtained, and the interfacial shear strength at the glass / resin interface is evaluated therefrom. The concept of measurement is shown in FIG.
The obtained interfacial shear strength is shown in Table 2.
[0078]
[Table 2]
[0079]
Experimental Example 12:
500 g of an aqueous solution of the silanol group-containing water-soluble aminosilane compound obtained in Experimental Example 1 was replaced with 80.0 g, 195.8 g of methacrylic acid was replaced with 75.4 g of 2-acrylamido-2-methylpropanesulfonic acid (the following compound), A silanol group-containing water-soluble methacrylsilane compound was synthesized according to Experimental Example 2 except that 0.038 g of p-methoxyphenol was added as a polymerization inhibitor.
[0080]
Experimental Example 13:
Except that 500 g of the aqueous solution of the silanol group-containing water-soluble aminosilane compound obtained in Experimental Example 1 was replaced with 22.1 g, and 195.8 g of methacrylic acid was replaced with 13.4 g of 2,2-dimethylpropionic acid (the following compound). A silanol group-containing water-soluble silane compound was synthesized according to Experimental Example 2.
[0081]
Experimental Example 14:
Similar to Experimental Example 2 except that 500 g of the aqueous solution of the silanol group-containing water-soluble aminosilane compound obtained in Experimental Example 1 was replaced with 22.1 g, and 195.8 g of methacrylic acid was replaced with 12.2 g of benzoic acid (the following compound). A silanol group-containing water-soluble silane compound was synthesized.
[0082]
Experimental Example 15-1:
Experimental example except that 500 g of the aqueous solution of the silanol group-containing water-soluble aminosilane compound obtained in Experimental Example 1 was replaced with 22.1 g, and 195.8 g of methacrylic acid was replaced with 13.8 g of 4-hydroxybenzoic acid (the following compound). According to 2, a water-soluble silane compound containing a silanol group was synthesized.
[0083]
Experimental Example 15-2:
Except that 500 g of the aqueous solution of the silanol group-containing water-soluble aminosilane compound obtained in Experimental Example 1 was replaced with 20.0 g, and 195.8 g of methacrylic acid was replaced with 14.1 g of 3,4-dihydroxybenzoic acid (the following compound). A silanol group-containing water-soluble silane compound was synthesized according to Experimental Example 2.
[0084]
Experimental Example 15-3:
The aqueous solution 500 g of the silanol group-containing water-soluble aminosilane compound obtained in Experimental Example 1 was replaced with 20.0 g, and 195.8 g of methacrylic acid was replaced with 17.2, g of 3,4,5-trihydroxybenzoic acid (the following compound). Except for the above, a silanol group-containing water-soluble silane compound was synthesized according to Experimental Example 2.
[0085]
Experimental Example 16:
Similar to Experimental Example 2 except that 500 g of the aqueous solution of the silanol group-containing water-soluble aminosilane compound obtained in Experimental Example 1 was replaced with 10.0 g, and 195.8 g of methacrylic acid was replaced with 2.87 g of oxalic acid dihydrate. The operation was performed.
A colorless and transparent aqueous solution was obtained. The aqueous solution did not become cloudy even after being left for one week or longer. Further, no peak of volatile organic solvent was observed.
[0086]
Experimental Example 17:
Similar to Experimental Example 2 except that 500 g of the aqueous solution of the silanol group-containing water-soluble aminosilane compound obtained in Experimental Example 1 was replaced with 10.0 g, and 195.8 g of methacrylic acid was replaced with 2.68 g of succinic acid (the following compound). A silanol group-containing water-soluble silane compound was synthesized.
[0087]
Experimental Example 18
Similar to Experimental Example 2, except that 500 g of the aqueous solution of silanol group-containing water-soluble aminosilane compound obtained in Experimental Example 1 was replaced with 10.0 g, and 195.8 g of methacrylic acid was replaced with 3.32 g of adipic acid (the following compound). A silanol group-containing water-soluble silane compound was synthesized.
[0088]
Experimental Example 19:
Similar to Experimental Example 2, except that 500 g of the aqueous solution of the silanol group-containing water-soluble aminosilane compound obtained in Experimental Example 1 was replaced with 10.0 g, and 195.8 g of methacrylic acid was replaced with 3.78 g of terephthalic acid (the following compound). A silanol group-containing water-soluble silane compound was synthesized.
[0089]
Experimental Example 20:
10.0 g of an aqueous solution of the silanol group-containing water-soluble aminosilane compound obtained in Experimental Example 1 was added to 10.0 g, and 195.8 g of methacrylic acid was added to meso-butane-1,2,3,4-tetracarboxylic acid (the following compound) 2 A silanol group-containing water-soluble silane compound was synthesized according to Experimental Example 2 except that the amount was changed to .66 g.
[0090]
Experimental Example 21:
In Example 2, except that 500 g of the aqueous solution of the silanol group-containing water-soluble aminosilane compound obtained in Example 1 was replaced with 10.0 g, and 195.8 g of methacrylic acid was replaced with 4.19 g of thioglycolic acid (the following compound). Accordingly, a silanol group-containing water-soluble silane compound was synthesized.
[0091]
Experimental Example 22:
Similar to Experimental Example 2 except that 500 g of the aqueous solution of the silanol group-containing water-soluble aminosilane compound obtained in Experimental Example 1 was replaced with 10.0 g, and 195.8 g of methacrylic acid was replaced with 3.41 g of thiomalic acid (the following compound). A silanol group-containing water-soluble silane compound was synthesized.
[0092]
Experimental Example 23:
The aqueous solution 500 g of the silanol group-containing water-soluble aminosilane compound obtained in Experimental Example 1 was replaced with 10.0 g, and 195.8 g of methacrylic acid was replaced with 4.78 g of 3,3′-dithiodipropionic acid (the following compound). A silanol group-containing water-soluble silane compound was synthesized according to Experimental Example 2 except for the above.
[0093]
Experimental Example 24:
Other than replacing 500 g of the aqueous solution of the silanol group-containing water-soluble aminosilane compound obtained in Experimental Example 1 with 10.0 g and 195.8 g of methacrylic acid with 6.96 g of 2,2′-dithiodibenzoic acid (the following compound). Synthesized a water-soluble silane compound containing a silanol group according to Experimental Example 2.
[0094]
Experimental Example 25:
In Example 2 except that 500 g of the aqueous solution of the silanol group-containing water-soluble aminosilane compound obtained in Example 1 was replaced with 20.0 g, and 195.8 g of methacrylic acid was replaced with 14.2 g of benzenesulfonic acid (the following compound). Accordingly, a silanol group-containing water-soluble silane compound was synthesized.
[0095]
Experimental Example 26:
An experiment was conducted except that 500 g of the silanol group-containing water-soluble aminosilane compound aqueous solution obtained in Experimental Example 1 was replaced with 20.0 g, and 195.8 g of methacrylic acid was replaced with 15.6 g of 4-hydroxybenzenesulfonic acid (the following compound). According to Example 2, a silanol group-containing water-soluble silane compound was synthesized.
[0096]
Experimental Example 27: Synthesis of water-soluble diaminosilane compound aqueous solution containing silanol group
Using a flask with a capacity of 500 ml, 1000 g of 3-aminopropyltriethoxysilane (Syraace S330 manufactured by Chisso Corporation) was added to N- (2-aminoethyl) -3-aminopropyltrimethoxysilane (Syraace manufactured by Chisso Corporation). S320) The same operation as in Experimental Example 1 was performed except that 222 g was replaced with 81 g of pure water.
[0097]
Experimental Example 28:
500 g of the aqueous solution of the silanol group-containing water-soluble aminosilane compound obtained in Experimental Example 1 was changed to 10.0 g of the aqueous solution of the silanol group-containing water-soluble diaminosilane compound obtained in Experimental Example 27, and 195.8 g of methacrylic acid was changed to 2.82 g. A silanol group-containing water-soluble methacrylsilane compound was synthesized in accordance with Experimental Example 2 except that it was replaced.
A yellow transparent aqueous solution was obtained. The aqueous solution did not become cloudy even after being left for one week or longer. Moreover, the peak of the volatile organic solvent was not observed.
[0098]
Experimental Example 29:
500 g of the aqueous solution of the silanol group-containing water-soluble aminosilane compound obtained in Experimental Example 1 was changed to 10.0 g of the aqueous solution of the silanol group-containing water-soluble diaminosilane compound obtained in Experimental Example 27, and 195.8 g of methacrylic acid was changed to 5.64 g. A silanol group-containing water-soluble methacrylsilane compound was synthesized in accordance with Experimental Example 2 except that it was replaced.
A yellow transparent aqueous solution was obtained. The aqueous solution did not become cloudy even after being left for one week or longer. Moreover, the peak of the volatile organic solvent was not observed.
[0099]
Experimental Example 30:
500 g of the aqueous solution of the silanol group-containing water-soluble aminosilane compound obtained in Experimental Example 1 was added to 10.0 g of the aqueous solution of the silanol group-containing water-soluble diaminosilane compound obtained in Experimental Example 27, and 195.8 g of methacrylic acid was 2,2- A silanol group-containing water-soluble silane compound was synthesized according to Experimental Example 2 except that 4.4 g of dimethylolpropionic acid was used.
A yellow transparent aqueous solution was obtained. The aqueous solution did not become cloudy even after being left for one week or longer. Moreover, the peak of the volatile organic solvent was not observed.
[0100]
Experimental example 31:
500 g of the aqueous solution of the silanol group-containing water-soluble aminosilane compound obtained in Experimental Example 1 was added to 10.0 g of the aqueous solution of the silanol group-containing water-soluble diaminosilane compound obtained in Experimental Example 27, and 195.8 g of methacrylic acid was 2,2- The same operation as in Experimental Example 2 was carried out except that dimethylolpropionic acid was replaced with 8.8 g.
A yellow transparent aqueous solution was obtained. The aqueous solution did not become cloudy even after being left for one week or longer. Moreover, the peak of the volatile organic solvent was not observed.
[0101]
Experimental Example 32: Synthesis of aqueous solution of water-soluble diaminosilane compound containing silanol group
Using a flask with a capacity of 500 ml, 1000 g of 3-aminopropyltriethoxysilane (Syraace S330, manufactured by Chisso Corporation) was added to N- (2-aminoethyl) -3-aminopropylmethyldimethoxysilane (Syraace, manufactured by Chisso Corporation). S310) The same operation as in Experimental Example 1 was performed except that 206 g was replaced with 54 g of pure water.
[0102]
Experimental Example 33:
500 g of the aqueous solution of the silanol group-containing water-soluble aminosilane compound obtained in Experimental Example 1 was changed to 10.0 g of the aqueous solution of the silanol group-containing water-soluble diaminosilane compound obtained in Experimental Example 32, and 195.8 g of methacrylic acid was changed to 2.69 g. A silanol group-containing water-soluble methacrylsilane compound was synthesized in accordance with Experimental Example 2 except that it was replaced.
A yellow transparent aqueous solution was obtained. The aqueous solution did not become cloudy even after being left for one week or longer. Moreover, the peak of the volatile organic solvent was not observed.
[0103]
Experimental Example 34:
500 g of the aqueous solution of the silanol group-containing water-soluble aminosilane compound obtained in Experimental Example 1 was changed to 10.0 g of the aqueous solution of the silanol group-containing water-soluble diaminosilane compound obtained in Experimental Example 32, and 195.8 g of methacrylic acid was changed to 5.38 g. A silanol group-containing water-soluble methacrylic silane compound was synthesized according to Experimental Example 2 except that it was replaced.
A yellow transparent aqueous solution was obtained. The aqueous solution did not become cloudy even after being left for one week or longer. Moreover, the peak of the volatile organic solvent was not observed.
[0104]
Experimental Example 35: Preparation of test sample for microdroplet measurement
One silane-treated glass fiber obtained in Experimental Example 8 was fixed to the mount with an adhesive. 50 g of vinyl ester resin (Lipoxy R-806 manufactured by Showa Polymer Co., Ltd.) was placed in the cup. To this, 0.5 g of an accelerator (Rigolac accelerator E, manufactured by Showa Polymer Co., Ltd.) and 1 g of a curing agent (Permec N, manufactured by NOF Corporation) were sequentially added while stirring. After defoaming at room temperature, a small drop of resin was adhered to the glass fiber by applying a small amount of resin to the glass fiber using a micropartel. This was heated at 50 ° C. for 2 hours, at 80 ° C. for 2 hours, and at 120 ° C. for 4 hours to cure the resin to obtain a test sample for microdroplet measurement.
[0105]
Experimental Example 36: Surface treatment of glass fiber with silanol group-containing water-soluble acrylic silane compound aqueous solution
As in Experimental Example 8, 30 g of the silanol group-containing water-soluble acrylic silane compound aqueous solution synthesized in Experimental Example 12 and 970 g of pure water were put into a beaker, and stirred to dissolve uniformly to obtain a surface treatment agent. . Glass fibers (diameter: about 16 μm) cut to a length of about 30 cm were immersed in the surface treatment agent for 30 seconds and dried in an oven at 100 ° C. for 20 minutes to obtain surface-treated glass fibers.
[0106]
Experimental Example 37: Preparation of test sample for microdroplet measurement
The same microdroplet measurement as in Experimental Example 35, except that the silane-treated glass fiber obtained in Experimental Example 36 was used instead of the surface-treated glass fiber obtained in Experimental Example 8. A test sample was obtained.
[0107]
Experimental Example 38: Surface treatment of glass fiber with methacryl group-containing alkoxysilane compound aqueous solution
In the same manner as in Experimental Example 8, 10 g of 3-methacryloxypropyltrimethoxysilane (S710 manufactured by Chisso Corporation) and 990 g of acetic acid water adjusted to pH 4 were placed in a beaker and stirred with a magnetic stirrer to dissolve evenly. Thus, a surface treatment agent was obtained. Immediately after that, a glass fiber cut into a length of about 30 cm (about 16 μm in diameter) was immersed in the surface treatment agent for 30 seconds and dried in an oven at 100 ° C. for 20 minutes to obtain a surface-treated glass fiber. It was.
[0108]
Experimental Example 39: Preparation of test sample for microdroplet measurement
The same microdroplet measurement as in Experimental Example 35 except that the surface-treated glass fiber obtained in Experimental Example 38 was used instead of the surface-treated glass fiber obtained in Experimental Example 8. A test sample was obtained.
[0109]
Experimental Example 40: Preparation of microdroplet measurement test sample
A test sample for microdroplet measurement was obtained in the same manner as in Experimental Example 35 except that the glass fiber was used as it was without surface treatment.
[0110]
Experimental Example 41: Microdroplet measurement
Microdroplet measurement was performed on the samples obtained in Experimental Example 35, Experimental Example 37, Experimental Example 39, and Experimental Example 40 using a composite material interface property evaluation apparatus HM410 (manufactured by Toei Sangyo Co., Ltd.). The measurement was performed in the same manner as in Example 11.
The obtained interfacial shear strength is shown in Table 3.
[0111]
[Table 3]
From these experimental examples, the silanol group-containing compound of the present invention has an excellent characteristic that maintains a stable state and has sufficient effect as a silane coupling agent even when stored for a long time in an aqueous solution state. Is shown to be a compound having
[0112]
【The invention's effect】
Even if the silanol group-containing compound aqueous solution of the present invention is stored for a long time in the state of an aqueous solution, the condensation of the silanol group-containing compounds can be maintained in a stable state without proceeding at a certain rate or more. Furthermore, it is a compound with excellent characteristics that has a sufficient effect as a surface treating agent. Further, the production method of the present invention can completely hydrolyze the compound obtained by the neutralization reaction without making the aqueous solution of the compound obtained by the neutralization reaction acidic.
The surface treatment agent of the present invention is suitable for glass fiber treatment, surface treatment of fillers such as talc and mica, casting molds, resin concrete, resin surface modification and water-based paint additives.
[Brief description of the drawings]
1 is a conceptual diagram of microdroplet measurement.
Claims (9)
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