CN115637586A - Surface treatment agent, glass cloth, and prepreg - Google Patents
Surface treatment agent, glass cloth, and prepreg Download PDFInfo
- Publication number
- CN115637586A CN115637586A CN202210830547.9A CN202210830547A CN115637586A CN 115637586 A CN115637586 A CN 115637586A CN 202210830547 A CN202210830547 A CN 202210830547A CN 115637586 A CN115637586 A CN 115637586A
- Authority
- CN
- China
- Prior art keywords
- component
- silane coupling
- coupling agent
- group
- surface treating
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 239000011521 glass Substances 0.000 title claims abstract description 72
- 239000004744 fabric Substances 0.000 title claims abstract description 58
- 239000012756 surface treatment agent Substances 0.000 title claims abstract description 36
- 239000006087 Silane Coupling Agent Substances 0.000 claims abstract description 95
- 229920005989 resin Polymers 0.000 claims abstract description 63
- 239000011347 resin Substances 0.000 claims abstract description 63
- 239000000203 mixture Substances 0.000 claims abstract description 53
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 51
- 239000011159 matrix material Substances 0.000 claims abstract description 43
- 125000003545 alkoxy group Chemical group 0.000 claims abstract description 15
- 239000004094 surface-active agent Substances 0.000 claims abstract description 15
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims abstract description 8
- 125000003700 epoxy group Chemical group 0.000 claims abstract description 6
- 125000001453 quaternary ammonium group Chemical group 0.000 claims abstract description 6
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 claims abstract description 6
- -1 vinylbenzyl Chemical group 0.000 claims description 32
- 150000001875 compounds Chemical class 0.000 claims description 26
- 239000007788 liquid Substances 0.000 claims description 24
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 18
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 8
- 239000002253 acid Substances 0.000 claims description 8
- 230000007062 hydrolysis Effects 0.000 claims description 8
- 238000006460 hydrolysis reaction Methods 0.000 claims description 8
- 125000000217 alkyl group Chemical group 0.000 claims description 7
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 6
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 claims description 6
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 6
- XDLMVUHYZWKMMD-UHFFFAOYSA-N 3-trimethoxysilylpropyl 2-methylprop-2-enoate Chemical group CO[Si](OC)(OC)CCCOC(=O)C(C)=C XDLMVUHYZWKMMD-UHFFFAOYSA-N 0.000 claims description 5
- NKSJNEHGWDZZQF-UHFFFAOYSA-N ethenyl(trimethoxy)silane Chemical compound CO[Si](OC)(OC)C=C NKSJNEHGWDZZQF-UHFFFAOYSA-N 0.000 claims description 5
- BPSIOYPQMFLKFR-UHFFFAOYSA-N trimethoxy-[3-(oxiran-2-ylmethoxy)propyl]silane Chemical compound CO[Si](OC)(OC)CCCOCC1CO1 BPSIOYPQMFLKFR-UHFFFAOYSA-N 0.000 claims description 5
- 229910052736 halogen Inorganic materials 0.000 claims description 3
- 125000005843 halogen group Chemical group 0.000 claims description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 2
- 229910052799 carbon Inorganic materials 0.000 claims description 2
- 239000007864 aqueous solution Substances 0.000 abstract description 14
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 21
- 239000002904 solvent Substances 0.000 description 15
- 238000011156 evaluation Methods 0.000 description 14
- 230000000052 comparative effect Effects 0.000 description 12
- 238000012360 testing method Methods 0.000 description 12
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 9
- 235000014113 dietary fatty acids Nutrition 0.000 description 9
- 229930195729 fatty acid Natural products 0.000 description 9
- 239000000194 fatty acid Substances 0.000 description 9
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 8
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 description 8
- 229920001955 polyphenylene ether Polymers 0.000 description 8
- 239000000126 substance Substances 0.000 description 8
- 238000005259 measurement Methods 0.000 description 7
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 6
- 238000000034 method Methods 0.000 description 6
- 239000000243 solution Substances 0.000 description 6
- ACAZETZQOYMARV-UHFFFAOYSA-N 3-[3-(ethenylamino)propyl-dimethoxysilyl]oxy-4-phenylbutan-1-amine hydrochloride Chemical compound Cl.C(=C)NCCC[Si](OC(CCN)CC1=CC=CC=C1)(OC)OC ACAZETZQOYMARV-UHFFFAOYSA-N 0.000 description 5
- 150000005215 alkyl ethers Chemical class 0.000 description 5
- 238000010292 electrical insulation Methods 0.000 description 5
- 150000004665 fatty acids Chemical class 0.000 description 5
- 239000011229 interlayer Substances 0.000 description 5
- 239000004727 Noryl Substances 0.000 description 4
- 229920001207 Noryl Polymers 0.000 description 4
- 125000004432 carbon atom Chemical group C* 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 239000007787 solid Substances 0.000 description 4
- 238000004381 surface treatment Methods 0.000 description 4
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 3
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 3
- 229910019142 PO4 Inorganic materials 0.000 description 3
- 239000002736 nonionic surfactant Substances 0.000 description 3
- 235000021317 phosphate Nutrition 0.000 description 3
- 229920002503 polyoxyethylene-polyoxypropylene Polymers 0.000 description 3
- 239000012779 reinforcing material Substances 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- 238000003860 storage Methods 0.000 description 3
- 238000009736 wetting Methods 0.000 description 3
- KOMNUTZXSVSERR-UHFFFAOYSA-N 1,3,5-tris(prop-2-enyl)-1,3,5-triazinane-2,4,6-trione Chemical compound C=CCN1C(=O)N(CC=C)C(=O)N(CC=C)C1=O KOMNUTZXSVSERR-UHFFFAOYSA-N 0.000 description 2
- LZMNXXQIQIHFGC-UHFFFAOYSA-N 3-[dimethoxy(methyl)silyl]propyl 2-methylprop-2-enoate Chemical compound CO[Si](C)(OC)CCCOC(=O)C(C)=C LZMNXXQIQIHFGC-UHFFFAOYSA-N 0.000 description 2
- URDOJQUSEUXVRP-UHFFFAOYSA-N 3-triethoxysilylpropyl 2-methylprop-2-enoate Chemical compound CCO[Si](OCC)(OCC)CCCOC(=O)C(C)=C URDOJQUSEUXVRP-UHFFFAOYSA-N 0.000 description 2
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 239000003945 anionic surfactant Substances 0.000 description 2
- 239000003093 cationic surfactant Substances 0.000 description 2
- 238000004140 cleaning Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000003822 epoxy resin Substances 0.000 description 2
- FWDBOZPQNFPOLF-UHFFFAOYSA-N ethenyl(triethoxy)silane Chemical compound CCO[Si](OCC)(OCC)C=C FWDBOZPQNFPOLF-UHFFFAOYSA-N 0.000 description 2
- 125000000524 functional group Chemical group 0.000 description 2
- 238000010030 laminating Methods 0.000 description 2
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 2
- 150000007524 organic acids Chemical class 0.000 description 2
- 230000035515 penetration Effects 0.000 description 2
- 229920000647 polyepoxide Polymers 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- FZHAPNGMFPVSLP-UHFFFAOYSA-N silanamine Chemical compound [SiH3]N FZHAPNGMFPVSLP-UHFFFAOYSA-N 0.000 description 2
- 150000004756 silanes Chemical class 0.000 description 2
- JXUKBNICSRJFAP-UHFFFAOYSA-N triethoxy-[3-(oxiran-2-ylmethoxy)propyl]silane Chemical compound CCO[Si](OCC)(OCC)CCCOCC1CO1 JXUKBNICSRJFAP-UHFFFAOYSA-N 0.000 description 2
- 230000004580 weight loss Effects 0.000 description 2
- JYEUMXHLPRZUAT-UHFFFAOYSA-N 1,2,3-triazine Chemical compound C1=CN=NN=C1 JYEUMXHLPRZUAT-UHFFFAOYSA-N 0.000 description 1
- XQUPVDVFXZDTLT-UHFFFAOYSA-N 1-[4-[[4-(2,5-dioxopyrrol-1-yl)phenyl]methyl]phenyl]pyrrole-2,5-dione Chemical compound O=C1C=CC(=O)N1C(C=C1)=CC=C1CC1=CC=C(N2C(C=CC2=O)=O)C=C1 XQUPVDVFXZDTLT-UHFFFAOYSA-N 0.000 description 1
- XNWFRZJHXBZDAG-UHFFFAOYSA-N 2-METHOXYETHANOL Chemical compound COCCO XNWFRZJHXBZDAG-UHFFFAOYSA-N 0.000 description 1
- DOYKFSOCSXVQAN-UHFFFAOYSA-N 3-[diethoxy(methyl)silyl]propyl 2-methylprop-2-enoate Chemical compound CCO[Si](C)(OCC)CCCOC(=O)C(C)=C DOYKFSOCSXVQAN-UHFFFAOYSA-N 0.000 description 1
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 239000004697 Polyetherimide Substances 0.000 description 1
- 229920001214 Polysorbate 60 Polymers 0.000 description 1
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical group [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- 229930006000 Sucrose Natural products 0.000 description 1
- ULUAUXLGCMPNKK-UHFFFAOYSA-N Sulfobutanedioic acid Chemical class OC(=O)CC(C(O)=O)S(O)(=O)=O ULUAUXLGCMPNKK-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 150000003973 alkyl amines Chemical class 0.000 description 1
- 150000008051 alkyl sulfates Chemical class 0.000 description 1
- 125000002947 alkylene group Chemical group 0.000 description 1
- 239000002280 amphoteric surfactant Substances 0.000 description 1
- 239000003242 anti bacterial agent Substances 0.000 description 1
- 239000002518 antifoaming agent Substances 0.000 description 1
- 239000002216 antistatic agent Substances 0.000 description 1
- 150000001805 chlorine compounds Chemical class 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000011960 computer-aided design Methods 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 239000011889 copper foil Substances 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 230000002950 deficient Effects 0.000 description 1
- 125000005265 dialkylamine group Chemical group 0.000 description 1
- OTARVPUIYXHRRB-UHFFFAOYSA-N diethoxy-methyl-[3-(oxiran-2-ylmethoxy)propyl]silane Chemical compound CCO[Si](C)(OCC)CCCOCC1CO1 OTARVPUIYXHRRB-UHFFFAOYSA-N 0.000 description 1
- 238000007865 diluting Methods 0.000 description 1
- 239000012895 dilution Substances 0.000 description 1
- 238000010790 dilution Methods 0.000 description 1
- WHGNXNCOTZPEEK-UHFFFAOYSA-N dimethoxy-methyl-[3-(oxiran-2-ylmethoxy)propyl]silane Chemical compound CO[Si](C)(OC)CCCOCC1CO1 WHGNXNCOTZPEEK-UHFFFAOYSA-N 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- MBGQQKKTDDNCSG-UHFFFAOYSA-N ethenyl-diethoxy-methylsilane Chemical compound CCO[Si](C)(C=C)OCC MBGQQKKTDDNCSG-UHFFFAOYSA-N 0.000 description 1
- ZLNAFSPCNATQPQ-UHFFFAOYSA-N ethenyl-dimethoxy-methylsilane Chemical compound CO[Si](C)(OC)C=C ZLNAFSPCNATQPQ-UHFFFAOYSA-N 0.000 description 1
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 1
- 239000011888 foil Substances 0.000 description 1
- NVVZQXQBYZPMLJ-UHFFFAOYSA-N formaldehyde;naphthalene-1-sulfonic acid Chemical compound O=C.C1=CC=C2C(S(=O)(=O)O)=CC=CC2=C1 NVVZQXQBYZPMLJ-UHFFFAOYSA-N 0.000 description 1
- 235000019253 formic acid Nutrition 0.000 description 1
- 238000001879 gelation Methods 0.000 description 1
- 150000002334 glycols Chemical class 0.000 description 1
- LNEPOXFFQSENCJ-UHFFFAOYSA-N haloperidol Chemical compound C1CC(O)(C=2C=CC(Cl)=CC=2)CCN1CCCC(=O)C1=CC=C(F)C=C1 LNEPOXFFQSENCJ-UHFFFAOYSA-N 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- 230000001771 impaired effect Effects 0.000 description 1
- 230000006698 induction Effects 0.000 description 1
- 238000009413 insulation Methods 0.000 description 1
- 239000000314 lubricant Substances 0.000 description 1
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 1
- 239000011976 maleic acid Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-M methacrylate group Chemical group C(C(=C)C)(=O)[O-] CERQOIWHTDAKMF-UHFFFAOYSA-M 0.000 description 1
- 125000005395 methacrylic acid group Chemical group 0.000 description 1
- 239000003595 mist Substances 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 238000006384 oligomerization reaction Methods 0.000 description 1
- 239000005416 organic matter Substances 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 238000004806 packaging method and process Methods 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 229920003192 poly(bis maleimide) Polymers 0.000 description 1
- 229920001601 polyetherimide Polymers 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 229920001721 polyimide Polymers 0.000 description 1
- 239000009719 polyimide resin Substances 0.000 description 1
- 239000003755 preservative agent Substances 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 239000011342 resin composition Substances 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000002356 single layer Substances 0.000 description 1
- 238000002791 soaking Methods 0.000 description 1
- HUAUNKAZQWMVFY-UHFFFAOYSA-M sodium;oxocalcium;hydroxide Chemical compound [OH-].[Na+].[Ca]=O HUAUNKAZQWMVFY-UHFFFAOYSA-M 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 239000005720 sucrose Substances 0.000 description 1
- 150000003871 sulfonates Chemical class 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 229920005992 thermoplastic resin Polymers 0.000 description 1
- 229920001187 thermosetting polymer Polymers 0.000 description 1
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 1
- 125000005270 trialkylamine group Chemical group 0.000 description 1
- 229920006337 unsaturated polyester resin Polymers 0.000 description 1
- 238000009941 weaving Methods 0.000 description 1
- 239000004711 α-olefin Substances 0.000 description 1
Landscapes
- Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)
- Surface Treatment Of Glass Fibres Or Filaments (AREA)
Abstract
The invention provides a glass cloth and a prepreg, which can increase the affinity and the adhesiveness between the glass cloth and a matrix resin and further can improve the heat resistance of a printed circuit wiring board, and can be produced to provide a surface treatment agent with excellent stability of a surface treatment agent aqueous solution. A surface treating agent comprising: a silane coupling agent composition containing at least two components selected from the group consisting of a component a, a component B, a component C and a component D, wherein the component a is a silane coupling agent having an alkoxy group and a quaternary ammonium cation, the component B is a silane coupling agent having an alkoxy group and a (meth) acrylic group, the component C is a silane coupling agent having a vinyl group, and the component D is a silane coupling agent having an epoxy group; and a surfactant.
Description
Technical Field
The present invention relates to a surface treatment agent for glass cloth, a glass cloth, and a prepreg, which are used for a printed wiring board of an electric or electronic device, a computer, or the like.
Background
In the past, printed circuit wiring boards generally consisted mainly of a composite of an inorganic reinforcing material and a matrix resin, and glass cloth was most commonly used as the inorganic reinforcing material. In recent years, as a matrix resin, a mixture of polyphenylene ether (PPE) and an epoxy resin or the like having a low dielectric constant and a low dielectric loss tangent has been used in order to reduce the dielectric constant and the dielectric loss tangent of a printed circuit wiring board (for example, see patent document 1). More specifically, a so-called prepreg is prepared by impregnating a glass cloth with a matrix resin, and the prepreg is laminated by stacking 1 or more sheets of the prepreg and further stacking a metal foil thereon to form a base material of a printed wiring board. In the production of the base material for the printed wiring board, the glass cloth has been previously subjected to a surface treatment with a silane coupling agent for the purpose of improving the affinity and adhesion between the glass cloth and the matrix resin.
The silane coupling agent generally has a structure in which an organic functional group and 2 to 3 alkoxy groups are bonded to a silicon atom, the alkoxy groups are hydrolyzed to form an alkylene oxide bond with the surface of the glass cloth, and the organic functional group reacts with the matrix resin to crosslink the glass cloth and the matrix resin. Therefore, the alkoxy group of the silane coupling agent needs to be hydrolyzed. Therefore, as a surface treatment agent for conventional glass cloth containing the silane coupling agent, a surface treatment agent obtained by dissolving a silane coupling agent in a mixed solution of water and a hydrolysis assistant is often used. As the hydrolysis assistant in this case, an organic acid such as acetic acid or formic acid can be used.
However, such conventional surface treatment agents for glass cloth (hereinafter, may be simply referred to as "treatment agents") have a problem that hydrolyzed silane compounds are polymerized with each other in the treatment agent, or that residual silane compounds are polymerized with each other and oligomerized when the treatment agent is impregnated or applied to the glass cloth. If oligomerization occurs, the adhesion between the glass cloth and the matrix resin becomes insufficient. Further, it is important to improve affinity and adhesion between the glass cloth and the matrix resin by the treating agent, but this is not a sufficient performance in the treating agents heretofore (for example, see patent document 2). As a result, the printed wiring board obtained has insufficient moisture absorption and heat resistance, and has a problem in properties such as peeling.
[ patent document 1] Japanese patent laid-open No. 2021-77786
[ patent document 2] International publication No. 2019/167391
Disclosure of Invention
[ problems to be solved by the invention ]
The invention provides a surface treatment agent which can improve the affinity and the adhesion between glass cloth and matrix resin and further can improve the electric insulation reliability of a printed circuit wiring substrate.
[ means for solving the problems ]
The present inventors have made diligent studies to solve the problems. As a result, they have found that a silane coupling agent composition containing at least two components selected from the group consisting of a silane coupling agent (component a) having an alkoxy group and a quaternary ammonium cation, a silane coupling agent (component B) having an alkoxy group and a (meth) acrylic group, a silane coupling agent (component C) having a vinyl group, and a silane coupling agent (component D) having an epoxy group is water-soluble, and therefore can be used as a surface treating agent for glass cloth in the same manner as conventional amino silane coupling agents, and that affinity or adhesion between glass cloth and a matrix resin is improved as compared with conventional amino silane coupling agents, and adhesion between glass cloth and a matrix resin is improved, whereby interlayer peeling of a printed wiring board can be prevented, and electrical insulation reliability of the printed wiring board can be improved. Based on these findings, the present invention has been completed.
The present invention is constituted as follows.
[1] A surface treating agent comprising: a silane coupling agent composition containing at least two components selected from a component A, a component B, a component C and a component D, wherein the component A is a silane coupling agent having an alkoxy group and a quaternary ammonium cation, the component B is a silane coupling agent having an alkoxy group and a (meth) acrylic group, the component C is a silane coupling agent having a vinyl group, and the component D is a silane coupling agent having an epoxy group; and a surfactant.
[2] The surface treating agent according to [1], wherein the component A is at least one compound selected from the group consisting of the compound represented by the formula (1) and the compound represented by the formula (2), the component B is at least one compound selected from the group consisting of the compound represented by the formula (3), the component C is at least one compound selected from the group consisting of the compound represented by the formula (4), and the component D is at least one compound selected from the group consisting of the compound represented by the formula (5).
In the formulae (1) to (5), X is vinylbenzyl, Y is halogen, R 1 、R 3 、R 5 、R 7 And R 9 Independently an alkyl group of carbon number 1 to 4, R 2 、R 4 、R 6 、R 8 And R 10 Independently methyl, ethyl or isopropyl, m is 0, 1 or 2, n is 0, 1 or 2.
[3] The surface-treating agent according to item [1] or [2], wherein the component A is N-vinylbenzyl-aminoethyl- γ -aminopropyltrialkoxysilane hydrochloride, the component B is 3-methacryloxypropyltrimethoxysilane, the component C is vinyltrimethoxysilane, and the component D is 3-glycidyloxypropyltrimethoxysilane.
[4] The surface treating agent according to any one of [1] to [3], wherein the silane coupling agent composition comprises the component A,
further comprises at least one component selected from the group consisting of component B, component C and component D.
[5] The surface treating agent according to [4], wherein the proportions of the components in the silane coupling agent composition are such that, assuming that the weight of the component A is 100 parts by weight, the component B is 0 to 100 parts by weight, the component C is 0 to 100 parts by weight, the component D is 0 to 100 parts by weight, and any one of the components B, C and D is not 0 part by weight.
[6] The surface treating agent according to [4] or [5], wherein the silane coupling agent composition comprises the component A, the component B and the component C.
[7] The surface treating agent according to [4] or [5], wherein the silane coupling agent composition comprises the component A, the component B, the component C and the component D.
[8] The surface treating agent according to any one of [1] to [3], wherein the silane coupling agent composition comprises a component B,
further comprises at least one component selected from the group consisting of component C and component D.
[9] The surface treating agent according to [8], wherein the silane coupling agent composition comprises a component B and a component D.
[10] The surface treating agent according to [8], wherein the silane coupling agent composition comprises a component B, a component C and a component D.
[11] The surface-treating agent according to any one of [1] to [10], wherein the silane coupling agent composition is converted into a prehydrolysis liquid by adding water.
[12] The surface treating agent according to [11], wherein the pre-hydrolysis liquid contains an acid.
[13] The surface treating agent according to [12], wherein the pH value of the prehydrolysis liquid is 3 to 7.
[14] A glass cloth which is surface-treated with the surface-treating agent according to any one of [1] to [13 ].
[15] A prepreg obtained by impregnating a glass cloth according to [14] with a matrix resin.
[ Effect of the invention ]
The stability and operability of the surface treatment agent are improved, and the affinity and adhesion between the glass cloth and the matrix resin are improved. A surface treatment agent which can be effectively used as a surface treatment agent for glass cloth, and which can prevent interlayer peeling of a printed wiring board by improving the adhesion between the glass cloth and a matrix resin, and can improve the electrical insulation reliability of the printed wiring board.
Detailed Description
The surface treatment agent of the present invention comprises: a silane coupling agent composition containing at least two components selected from the group consisting of a silane coupling agent (component A) having an alkoxy group and a quaternary ammonium cation, a silane coupling agent (component B) having an alkoxy group and a (meth) acrylic group, a silane coupling agent (component C) having a vinyl group, and a silane coupling agent (component D) having an epoxy group; and a surfactant. In the present specification, the (meth) acrylic group means either or both of an acrylic group and a methacrylic group.
Examples of the silane coupling agent having an alkoxy group and a quaternary ammonium cation as the component A include compounds represented by formula (1) and compounds represented by formula (2).
In the formula (1) and the formula (2), X is vinylbenzyl, Y is halogen, R 1 And R 3 Each is an alkyl group having 1 to 4 carbon atoms, R 2 And R 4 Respectively methyl, ethyl or isopropyl, and n is 0, 1 or 2.
Examples of the vinylbenzyl-aminopropyltrialkoxysilane hydrochloride or vinylbenzyl-aminopropylalkyldialkoxysilane hydrochloride represented by formula (1) include: vinylbenzyl-aminopropyltrimethoxysilane hydrochloride, vinylbenzyl-aminopropyltriethoxysilane hydrochloride, vinylbenzyl-aminopropylmethyldimethoxysilane hydrochloride, and the like. Further, as the N-vinylbenzylaminoethyl- γ -aminopropylalkyldialkoxysilane hydrochloride or N-vinylbenzylaminoethyl- γ -aminopropyltrialkoxysilane hydrochloride represented by formula (2), there can be exemplified: n-vinylbenzyl-aminoethyl-gamma-aminopropylmethyldimethoxysilane hydrochloride, N-vinylbenzyl-aminoethyl-gamma-aminopropyltrimethoxysilane hydrochloride, N-vinylbenzyl-aminoethyl-gamma-aminopropyltriethoxysilane hydrochloride, and the like. Of these, N-vinylbenzyl-aminoethyl- γ -aminopropyltriethoxysilane hydrochloride and N-vinylbenzyl-aminoethyl- γ -aminopropyltrimethoxysilane hydrochloride are preferred. More preferred is N-vinylbenzyl-aminoethyl- γ -aminopropyltrimethoxysilane hydrochloride in terms of ease of acquisition and performance of the silane coupling agent composition obtained. These may be used alone or in combination of two or more kinds as the component A of the silane coupling agent composition of the present invention.
As commercially available products containing N-vinylbenzyl-aminoethyl- γ -aminopropyltrimethoxysilane hydrochloride, mention may be made of: s350 (JNC), KBM-575 (Kyue chemical industries, inc.), and Z-6032 (Dow-Toray).
The silane coupling agent having an alkoxy group and a (meth) acrylic group as the component B is a compound represented by the formula (3).
In the formula (3), R 5 Is alkyl of 1 to 4 carbon atoms, R 6 Is methyl, ethyl or isopropyl, and m is 0, 1 or 2.
Examples of the 3-methacryloxypropylalkoxysilane represented by the formula (3) include: 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropyltriethoxysilane, 3-methacryloxypropylmethyldimethoxysilane, 3-methacryloxypropylmethyldiethoxysilane, and the like. Among these, 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropyltriethoxysilane, and 3-methacryloxypropylmethyldimethoxysilane are preferable from the viewpoint of the ease of obtaining and the performance of the obtained silane coupling agent composition.
The silane coupling agent having a vinyl group as the component C includes a compound represented by the formula (4).
In the formula (4), R 7 Is alkyl of 1 to 4 carbon atoms, R 8 Is methyl, ethyl or isopropyl, and n is 0, 1 or 2.
Examples of the compound represented by the formula (4) include: vinyltrimethoxysilane, vinyltriethoxysilane, vinylmethyldimethoxysilane, vinylmethyldiethoxysilane, etc. Among these, vinyltrimethoxysilane and vinyltriethoxysilane are preferable in terms of the easiness of obtaining and the performance of the obtained silane coupling agent composition.
Examples of the silane coupling agent having an epoxy group as the component D include compounds represented by the formula (5).
In the formula (5), R 9 Is alkyl of 1 to 4 carbon atoms, R 10 Represents methyl, ethyl or isopropyl, and m is 0, 1 or 2.
Examples of the compound represented by the formula (5) include: 3-glycidyloxypropyltrimethoxysilane, 3-glycidyloxypropyltriethoxysilane, 3-glycidyloxypropylmethyldimethoxysilane, 3-glycidyloxypropylmethyldiethoxysilane and the like. Among these, 3-glycidoxypropyltrimethoxysilane and 3-glycidoxypropyltriethoxysilane are preferable in terms of ease of acquisition and performance of the silane coupling agent composition to be obtained.
The silane coupling agent composition used for the surface treatment agent of the present invention is obtained by mixing at least two components selected from the components a, B, C and D.
The silane coupling agent composition of the present invention is water-soluble, and therefore can be treated in the same manner as conventional silane coupling agents, and the obtained surface treatment agent is superior in stability as an aqueous solution to a conventional surface treatment agent using a silane coupling agent of vinylbenzylamino-based hydrochloride alone, and therefore can be easily treated. Further, the glass cloth surface-treated with the surface treatment agent of the present invention exhibits excellent affinity and adhesion to the matrix resin, and the adhesion is improved, whereby it is expected that the interlayer peeling of the printed wiring board is prevented, and the electrical insulation reliability of the printed wiring board is also improved.
The preferred embodiment of the present invention includes an embodiment containing the component a and further containing at least one component selected from the group consisting of the components B, C and D. The contents of the components B, C and D are in the range of 0 to 100 parts by weight, 0 to 100 parts by weight of the component B, 0 to 100 parts by weight of the component C and 0 to 100 parts by weight of the component D, respectively, based on 100 parts by weight of the component A. Wherein any one of the components B, C and D is not 0 part by weight.
When the component A and the component B or the component C are used, the proportion of each component in the silane coupling agent composition is preferably 50 to 80% by weight of the component A, 20 to 50% by weight of the total of the component B and the component C, more preferably 50 to 60% by weight of the component A, and 40 to 50% by weight of the total of the component B and the component C. When the components A and D are used, the ratio of the components A to D in the silane coupling agent composition is preferably 50 to 90% by weight, the ratio of the component D is preferably 10 to 50% by weight, and more preferably 75 to 90% by weight, and the ratio of the component D is preferably 10 to 25% by weight.
When the components A, B and C are used, the proportion of each component in the silane coupling agent composition is preferably 33 to 80 wt% for the component A, 10 to 50 wt% for the component B and 10 to 50 wt% for the component C, and more preferably 33 to 50 wt% for the component A, 20 to 40 wt% for the component B and 20 to 40 wt% for the component C. The silane coupling agent composition has a good balance between the aqueous solution stability and the permeation of the PPE resin.
When importance is placed on lowering the contact angle, the components a, B, C, and D are preferably used. In the silane coupling agent composition in this case, the ratio of the components A is preferably 25 to 70 wt%, the ratio of the component B is 5 to 25 wt%, the ratio of the component C is 5 to 50 wt%, the ratio of the component D is 5 to 25 wt%, and more preferably, the ratio of the component A is 40 to 60 wt%, the ratio of the component B is 5 to 15 wt%, the ratio of the component C is 20 to 40 wt%, and the ratio of the component D is 5 to 20 wt%.
In another preferred embodiment, the resin composition further contains component B and at least one component selected from component a, component C and component D. The silane coupling agent composition of the above form is particularly excellent in affinity with PPE resins. When importance is attached to the stability of the aqueous solution, the components B, C, and D are preferably used or the components B and D are preferably used, and more preferably the components B and D are used.
When the components B and C are used, the ratio of the component B to the component C is preferably 50 to 90 wt%, the ratio of the component C is preferably 10 to 50 wt%, and more preferably 65 to 75 wt%, and the ratio of the component C is 25 to 35 wt%.
When the components B, C and D are used, the proportion of each component in the silane coupling agent composition is preferably 50 to 80% by weight of the component B, 10 to 50% by weight of the component C, 3 to 30% by weight of the component D, more preferably 60 to 75% by weight of the component B, 20 to 40% by weight of the component C and 5 to 20% by weight of the component D.
When the component B and the component D are used, the proportion of each component in the silane coupling agent composition is preferably 10 to 40% by weight of the component B, 60 to 90% by weight of the component D, more preferably 10 to 30% by weight of the component B, and 70 to 90% by weight of the component D.
When the silane coupling agent is mixed, a solvent may not be used, but a solvent such as alcohol may be used as needed.
The surfactant used in the present invention may be a known surfactant. Any of an anionic surfactant, a cationic surfactant, and a nonionic surfactant can be used, and a nonionic surfactant is preferable in terms of workability, characteristics, and the like. Examples of the nonionic surfactant include: fatty acid glycerides, sorbitan fatty acid esters, sucrose fatty acid esters, polyoxyethylene alkyl ethers, polyoxyethylene polyoxypropylene alkyl ethers, polyoxyethylene alkylphenyl ethers, polyoxyethylene polyoxypropylene glycols, fatty acid polyethylene glycols, fatty acid polyoxyethylene sorbitan, fatty acid alkanolamides, and the like.
As the anionic surfactant, there may be mentioned: fatty acid monocarboxylates, polyoxyethylene alkyl ether carboxylates, N-acyl sarcosinates, N-acyl glutamates, dialkyl sulfosuccinates, alkane sulfonates, α -olefin sulfonates, linear alkylbenzene sulfonates, naphthalene sulfonate-formaldehyde condensates, alkyl naphthalene sulfonates, N-methyl-N-acyl taurates, alkyl sulfates, polyoxyethylene alkyl ether sulfates, fatty acid ester sulfates, alkyl phosphates, polyoxyethylene alkyl ether phosphates, polyoxyethylene alkylphenyl ether phosphates, and the like.
As the cationic surfactant, there can be mentioned: monoalkylamine salts, dialkylamine salts, trialkylamine salts, alkyltrimethylammonium chlorides, alkylbenzalkonium chlorides, and the like. Examples of the amphoteric surfactant include: alkyl betaines, fatty acid amide propyl betaines, 2-alkyl-N-carboxymethyl-N-hydroxyethyl imidazolinium betaines, alkyl diethylenetriamine acetic acid, alkyl amine oxides, and the like.
The surfactant may have a Hydrophilic-Lipophilic Balance (HLB) value of 6 to 19. Here, the HLB value of the surfactant can be calculated based on the chemical structure of the surfactant. Among them, the HLB value is preferably 10 or more, and the range of the HLB value is more preferably 13 to 15. A polyoxyethylene alkyl ether or a polyoxyethylene polyoxypropylene alkyl ether may be particularly preferably used. The concentration of the surfactant in the treating agent is preferably about 0.1g/L to 50.0g/L, and more preferably about 0.5g/L to 10.0g/L, in terms of solid content.
The surface treatment agent of the present invention is not particularly limited in composition, physical properties, and the like, as long as it contains the silane coupling agent composition used in the present invention. That is, the silane coupling agent composition of the present invention may be used as it is, or a liquid diluted with a solvent may be used as the treating agent. Preferably, the treatment agent is prepared by dilution with a solvent. The solvent may be an organic solvent such as alcohol or water, but water is preferred in terms of safety and hygiene. By using water as a solvent, a prehydrolysis liquid described later is obtained. When water is used as the solvent, it is preferable to adjust the pH to 3 to 7 by adding an acid in terms of storage stability of the treatment agent. The acid to be added at this time is not particularly limited, and acetic acid may be preferably used.
When water is used as the solvent, water is added to the silane coupling agent composition in a weight ratio of preferably 0.001 to 1, more preferably 0.001 to 0.1, and still more preferably 0.001 to 0.05, based on the total weight of the silane coupling agent composition, and the mixture is mixed to prepare a prehydrolysis solution, and the prehydrolysis solution is preferably prepared as it is or diluted to prepare a treatment agent. The silane coupling agent composition has improved solubility in water by being prepared as a prehydrolysis liquid. The treatment agent obtained by diluting the prehydrolysis liquid exhibits superior interfacial adhesion as compared with the treatment agent obtained without the prehydrolysis liquid. The water used as a constituent of the prehydrolysis liquid may preferably be pure water.
In order to obtain a homogeneous prehydrolysis liquid, an alcohol may be further added to the prehydrolysis liquid. The alcohol used is preferably methanol, ethanol, isopropanol, or the like. In the case where the alcohol is added, if the weight ratio is 0.02 to 5 relative to the total weight of the silane coupling agent composition, the prehydrolysis liquid and the treating agent prepared from the prehydrolysis liquid can be uniformly prepared.
The prehydrolysis solution may optionally be adjusted in pH by addition of acid to improve storage stability. Preferred acids are acetic acid, maleic acid, and the like. The pH of the prehydrolysis liquid is preferably 3 to 7, more preferably 3 to 5, and still more preferably 4 to 5. If the pH value is within the above range, the prehydrolysis liquid and the treatment agent prepared from the prehydrolysis liquid are transparent and uniform, and are less likely to cause cloudiness or gelation.
The prehydrolysis liquid is preferably produced by adding water and, if necessary, an alcohol and/or an acid to the silane coupling agent composition and stirring at room temperature (20 ℃ to 30 ℃) for 10 minutes to 2 hours. The stirring time is preferably 0.2 hour or more, and more preferably about 0.5 to 1 hour.
The surface treatment agent of the present invention may contain one or more other additives selected from pigments, antifoaming agents, lubricants, preservatives, pH adjusters, film forming agents, antistatic agents, antibacterial agents, dyes, and the like, in addition to the silane coupling agent composition, surfactant, solvent, and acid used in the present invention, as long as the effects of the present invention are not impaired.
The proportion of the silane coupling agent composition contained in the surface treatment agent of the present invention is preferably in the range of 0.01 to 40% by weight, and more preferably 0.01 to 10% by weight, in the surface treatment agent.
The method of treating the glass cloth with the surface treatment agent of the present invention may use a known method. Specifically, the treatment is carried out by immersing the glass cloth in the treatment agent or applying the treatment agent in a mist form to the glass cloth and heat-treating the glass cloth (for example, at about 100 to 150 ℃ for about 0.1 to 10 minutes). In this case, the amount of the silane coupling agent attached to the glass cloth is preferably about 0.030 to 0.300 wt%, and the amount of the surfactant attached to the glass cloth is preferably about 0.015 to 0.300 wt%. The sum of the amounts of the silane coupling agent and the surfactant adhering to the glass cloth is preferably about 0.045 wt% to about 0.600 wt%. The adhesion amount is a weight loss amount of the organic component measured by a loss on ignition test (described in Japanese Industrial Standards (JIS) specification R3420: 2013).
As the glass cloth as the inorganic reinforcing material, known glass cloth can be used. Specifically, it is preferable to use glass yarns obtained by bundling about 100 to about 800 monofilaments, each having a filament diameter of about 5 to about 10 μm, as the warp yarns and the weft yarns used for weaving the glass cloth. The weave structure includes a structure woven by a plain weave, a satin weave, a basket weave, a twill weave, or the like, and preferably a plain weave. As the kind of glass, E glass (alkali-free), D glass (low dielectric constant), T glass (high strength), C glass (soda lime), H glass (high dielectric constant), and the like used as a base material of a printed circuit wiring board can be used. Preferable examples thereof include EP03C, EP06, EP08A, EP11C, EP10A and EP18B described in JIS R3414.
The prepreg of the present invention can be produced by impregnating the glass cloth of the present invention obtained in the above manner with a matrix resin. The matrix resin may be a known resin. Specifically, there may be mentioned: thermosetting resins such as epoxy resins, unsaturated polyester resins, polyimide resins, bismaleimide Triazine (BT) resins, and thermoplastic resins such as PPE resins, polyetherimide resins, and fluororesins. The matrix resin may contain known additives such as a curing agent. The prepregs of the present invention may be used to produce single ply or laminated sheets. For example, a laminate sheet as a base material of a printed wiring board can be obtained by impregnating the glass cloth of the present invention with the matrix resin to prepare a prepreg, laminating a plurality of the prepregs in a predetermined number, placing copper foils on top and bottom, or laminating the prepregs on an inner core sheet, and molding the prepregs under heat and pressure.
When the glass cloth is impregnated with the matrix resin, the matrix resin is preferably dissolved in a solvent and used. The solvent is not limited as long as it can dissolve the matrix resin, and examples thereof include: toluene, acetone, methyl cellosolve, dimethylformamide, cyclohexanone, and the like. Toluene is generally used as a solvent when PPE resins are used.
In the single-layer sheet and the laminated sheet of the present invention, the adhesion between the glass cloth and the matrix resin is excellent. Therefore, the adhesion is improved as compared with a laminate using a glass cloth surface-treated with a conventional treating agent, thereby preventing interlayer peeling of the printed wiring board and improving the electrical insulation reliability of the printed wiring board.
[ examples ]
The present invention will be described in detail with reference to examples below, but the present invention is not limited to these examples. The symbols, chemical formulae and test methods of the compounds used in examples and comparative examples are as follows.
S350: a 40% methanol solution of N-vinylbenzyl-aminoethyl-gamma-aminopropyltrimethoxysilane hydrochloride (JNC).
S710: 3-Methacryloxypropyltrimethoxysilane (JNC).
S210: vinyltrimethoxysilane (manufactured by JNC).
S510: 3-glycidyloxypropyltrimethoxysilane (JNC).
The chemical formulas of S350, S710, S210 and S510 are respectively formula (2-1), formula (3-1), formula (4-1) and formula (5-1).
[ preparation of surface treatment agent (prehydrolysis liquid) ]
A silane coupling agent composition is prepared by using S350 as a component A, S710 as a component B, S210 as a component C, S510 as a component D, and two or more of the components A, B, C and D. The silane coupling agent composition is mixed with polyoxyethylene alkyl ether as a surfactant and pure water as a solvent. Further, acetic acid was used as an organic acid to adjust the pH to 4, thereby preparing a prehydrolysis liquid. The silane coupling agents used in the silane coupling agent compositions and the ratios thereof are shown in tables 1-1, 1-2, 2 and 3, together with the evaluation results in the examples.
[ surface treatment of glass slide ]
A colorless transparent slide glass satisfying JISR3703 was prepared. The prehydrolysis liquid was adjusted using pure water and acetic acid so that the concentration of the silane coupling agent became 1 wt% and used as a surface treatment agent. After the glass slide was immersed in the surface treatment agent, one side of the glass slide was held until no more drop was dropped, and further dried at 110 ℃ for 5 minutes to obtain a surface-treated glass slide of the present example.
[ surface treatment of glass cloth ]
Glass cloth of The Institute for interconnection and Packaging Electronic circuits, and industrial computer aided design (IPC) specification model (style) 7628 is subjected to heat cleaning (heat cleaning) to prepare glass cloth from which organic matter present on The surface of The glass cloth has been removed. The prehydrolysis liquid was adjusted using pure water and acetic acid to be used as a surface treatment agent so that the concentration of the silane coupling agent became 1 wt%. After the glass cloth was immersed in the surface treatment agent, the glass cloth was squeezed with a glass rod, and further dried at 110 ℃ for 5 minutes to obtain the surface-treated glass cloth of this example. The sum of the amounts of the silane coupling agent and the surfactant adhering to the glass cloth was calculated from the amount of weight loss of the organic component measured by the loss on ignition test, and was 0.20 wt%. The ignition loss test was carried out in accordance with JIS standard R3420: 2013.
[ preparation of matrix resin ]
As the matrix resin 1, there were used NORYL (NORYL) SA90 (manufactured by SABIC corporation) which is a polyphenylene ether resin having both terminal hydroxyl groups, jER1001 (manufactured by mitsubishi chemical corporation) which is a bisphenol a resin, jER154 (manufactured by mitsubishi chemical corporation) which is a polyfunctional resin, cyclohexanone as a solvent, a resin having a molecular weight of SA90: jER1001: jER154 is 110.94:100:10.94, the solid content was 56.8% by weight.
The matrix resin 2 was composed of jER1001 (manufactured by mitsubishi chemical corporation) as a bisphenol a resin, jER154 (manufactured by mitsubishi chemical corporation) as a polyfunctional resin, and cyclohexanone as a solvent, and was prepared in the following manner, wherein jER1001: jER154 is 100 by weight: 10.94, the solid content was 56.8% by weight.
As the matrix resin 3, NORYL (NORYL) SA9000 (manufactured by SABIC basic industries, inc.), a polyphenylene ether resin having methacrylate groups at both ends (SABIC), triallyl isocyanurate (manufactured by TCI), a cyclohexanone as a crosslinking assistant, a resin having a structure represented by SA9000: the weight ratio of triallyl isocyanurate is 70:30, the solid content was 56.8% by weight.
[ hydrolysis test ]
The prehydrolysis solution was adjusted using pure water and acetic acid so that the concentration of the silane coupling agent was 2 wt% and the pH was in the range of 3 to 5, and 500mL of the prehydrolysis solution was placed in a 1L beaker. The time until generation of white turbidity was observed by stirring at 300rpm with a mechanical stirrer while keeping the temperature at 30 ℃ in a water bath.
The treating agent exhibits the characteristics as a surface treating agent by being hydrolyzed by the silane coupling agent to crosslink the glass cloth and the matrix resin, but the hydrolyzed silane coupling agents gradually polymerize with each other to cause cloudiness. Since workability and properties of the surface treatment agent deteriorate when the silane coupling agents are polymerized with each other, the aqueous solution is preferably not easily clouded and stable for a long period of time. The longer the time until the occurrence of white turbidity, the better the stability of the aqueous solution, and in the present invention, the time until the occurrence of white turbidity is less than 20 hours, the poor stability of the aqueous solution is judged, the 20 hours or more is judged, and the 40 hours or more is judged to be good.
[ contact Angle measurement ]
Matrix resins 1 to 3 were dropped on the surface-treated glass slide using an 18G syringe needle, and the contact angle was measured 5 times, and the average value was used as the contact angle. For the measurement, an automatic contact angle meter DM-501 manufactured by KYOWA was used. The smaller the value of the contact angle, the better the wet spread of the matrix resin, and in the present invention, the value of the contact angle is judged to be poor if it is 35 ° or more, and is judged to be sufficient if it is less than 35 °.
[ wetting test ]
The glass cloth subjected to surface treatment was cut into a size of 5cm square to prepare a test piece. Then, the resin was floated on the matrix resins 1 to 3, and the degree of penetration (wet-out) of the matrix resin into the glass cloth after passing through the resin was evaluated in 5 stages (1 (defective) to 5 (good) induction evaluations). In the immersion humidity evaluation, 1 was judged to be poor, and 2 or more was judged to be sufficient.
In the present invention, when all of the aqueous solution stability, contact angle and wettability evaluations are acceptable, the overall evaluation is judged to be "acceptable", and when any one of them is not acceptable, the overall evaluation is judged to be "unacceptable".
Examples 1 to 11
Hydrolysis test, contact angle measurement, and wettability test were performed according to the methods described above. Matrix resin 1 was used as the matrix resin. The silane coupling agent composition of the surface treating agent used is shown in Table 1-1 or Table 1-2. The results are shown in Table 1-1 or Table 1-2.
Comparative examples 1 to 3
Surface treatment agents were prepared in the same manner as in examples 1 to 11, except that S350, S710, and S210 were used alone, and a hydrolysis test, a contact angle measurement, and a wettability test were performed by the same methods. The results of comparative examples 1 to 3 are shown in Table 1-2.
TABLE 1-1
TABLE 1-2
As shown in tables 1-1 and 1-2, in examples 1 to 11, the time until clouding occurred in the hydrolysis test was 20 hours or more, and the aqueous solution stability was satisfactory or good, and good aqueous solution stability was exhibited. The contact angle may be 30 ° or less. In particular, example 10 showed good wet spread at 22.7 °. The evaluation of the degree of wetting was 2 or more in all examples, and the evaluation was comprehensive. On the other hand, in comparative example 1, the contact angle measurement result was satisfactory, but it was slightly higher than that in the examples. The time until cloudiness occurred was short, 3 hours, and it was impossible to evaluate the wettability, and it was also impossible to evaluate the overall evaluation. The time until cloudiness occurred and the contact angle in comparative example 2 were acceptable, but the wettability was evaluated as unacceptable and the overall evaluation was unacceptable. The time until cloudiness occurred in comparative example 3 was 200 hours or more, which was good, and the contact angle measurement result was satisfactory. However, the contact angle was slightly higher than that of the examples. The degree of wetting was evaluated as impossible and the overall evaluation was evaluated as impossible.
Examples 12 to 30 and comparative examples 4 to 5
Contact angle measurement and wettability test were performed by the same methods as in examples 1 to 11, except that the matrix resin 1 was changed to the matrix resin 2 or the matrix resin 3. In the case of using the matrix resin 2 or 3, the comparative example is set to S350 in the same manner as the method disclosed in comparative example 1 of japanese patent application laid-open No. 2002-194670. The silane coupling agent composition of the surface treatment agent used is shown in table 2 or table 3. The results are shown in table 2 or table 3.
TABLE 2
TABLE 3
As shown in tables 2 and 3, the time until occurrence of white turbidity was 20 hours or more in examples 12 to 30, the stability of the aqueous solution was satisfactory or excellent, the contact angle was 35 ° or less and was acceptable, and the wettability was 2 or more and was acceptable, and the overall evaluation was possible. On the other hand, in comparative example 4, although the contact angle and the wettability were evaluated as acceptable, the contact angle was slightly higher than those of the examples. The time until cloudiness occurred was short, and was 3 hours, and the overall evaluation was impossible. In comparative example 5, the contact angle was not less than 38 ° and was also poor in addition to the poor stability of the aqueous solution, and the overall evaluation was impossible.
The embodiment of the invention can meet all of the stability, the wettability expansibility and the good soaking humidity of the aqueous solution. On the other hand, in the comparative example in which the silane coupling agent was used alone, any of the characteristics could not be satisfied.
The results show that the surface treatment agent obtained by the present invention is excellent in stability as an aqueous solution, exhibits excellent wet spreadability in various matrix resins, and is expected to improve adhesion by affinity such as penetration of the resin after the resin, and is effective as a surface treatment agent for glass cloth.
[ industrial applicability ]
The surface treatment agent of the present invention is excellent in storage stability, and therefore, the surface treatment agent is improved in handling properties, and the affinity between the glass cloth and the matrix resin is good, and therefore, the surface treatment agent is expected to improve the adhesion between the glass cloth and the matrix resin, prevent the interlayer peeling of the printed wiring board, and further improve the electrical insulation reliability of the printed wiring board.
Claims (15)
1. A surface treating agent comprising: a silane coupling agent composition containing at least two components selected from a component A, a component B, a component C and a component D, wherein the component A is a silane coupling agent having an alkoxy group and a quaternary ammonium cation, the component B is a silane coupling agent having an alkoxy group and a (meth) acrylic group, the component C is a silane coupling agent having a vinyl group, and the component D is a silane coupling agent having an epoxy group; and a surfactant.
2. The surface treating agent according to claim 1, wherein the component A is at least one compound selected from the group consisting of the compound represented by formula (1) and the compound represented by formula (2), the component B is at least one compound selected from the group consisting of the compound represented by formula (3), the component C is at least one compound selected from the group consisting of the compound represented by formula (4), and the component D is at least one compound selected from the group consisting of the compound represented by formula (5),
in the formulae (1) to (5), X is vinylbenzyl, Y is halogen, R 1 、R 3 、R 5 、R 7 And R 9 Independently an alkyl group of carbon number 1 to 4, R 2 、R 4 、R 6 、R 8 And R 10 Independently methyl, ethyl or isopropyl, m is 0, 1 or 2, n is 0, 1 or 2.
3. The surface treating agent according to claim 1 or 2, wherein the component A is N-vinylbenzyl-aminoethyl- γ -aminopropyltrialkoxysilane hydrochloride, the component B is 3-methacryloxypropyltrimethoxysilane, the component C is vinyltrimethoxysilane, and the component D is 3-glycidyloxypropyltrimethoxysilane.
4. The surface treating agent according to any one of claims 1 to 3, wherein the silane coupling agent composition comprises component A,
further comprises at least one component selected from the group consisting of the component B, the component C and the component D.
5. The surface treating agent according to claim 4, wherein the ratio of each component in the silane coupling agent composition is 0 to 100 parts by weight of the component B, 0 to 100 parts by weight of the component C, 0 to 100 parts by weight of the component D, and any one of the components B, C and D is not 0 part by weight, based on 100 parts by weight of the component A.
6. The surface treating agent according to claim 4 or 5, wherein the silane coupling agent composition comprises the components A, B and C.
7. The surface treating agent according to claim 4 or 5, wherein the silane coupling agent composition comprises the components A, B, C and D.
8. The surface treating agent according to any one of claims 1 to 3, wherein the silane coupling agent composition comprises a B component,
further comprises at least one component selected from the group consisting of component C and component D.
9. The surface treating agent according to claim 8, wherein the silane coupling agent composition comprises a component B and a component D.
10. The surface treating agent according to claim 8, wherein the silane coupling agent composition comprises a component B, a component C and a component D.
11. The surface treating agent according to any one of claims 1 to 10, wherein the silane coupling agent composition is made into a prehydrolysis liquid by adding water.
12. The surface treatment agent according to claim 11, wherein the pre-hydrolysis liquid contains an acid.
13. The surface treating agent according to claim 12, wherein the pH of the prehydrolysis liquid is 3 to 7.
14. A glass cloth surface-treated with the surface treating agent according to any one of claims 1 to 13.
15. A prepreg obtained by impregnating the glass cloth according to claim 14 with a matrix resin.
Applications Claiming Priority (4)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2021119876 | 2021-07-20 | ||
| JP2021-119876 | 2021-07-20 | ||
| JP2022-093444 | 2022-06-09 | ||
| JP2022093444A JP2023015993A (en) | 2021-07-20 | 2022-06-09 | Surface treatment agent |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN115637586A true CN115637586A (en) | 2023-01-24 |
Family
ID=84940778
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202210830547.9A Pending CN115637586A (en) | 2021-07-20 | 2022-07-15 | Surface treatment agent, glass cloth, and prepreg |
Country Status (2)
| Country | Link |
|---|---|
| CN (1) | CN115637586A (en) |
| TW (1) | TW202321353A (en) |
-
2022
- 2022-07-15 TW TW111126714A patent/TW202321353A/en unknown
- 2022-07-15 CN CN202210830547.9A patent/CN115637586A/en active Pending
Also Published As
| Publication number | Publication date |
|---|---|
| TW202321353A (en) | 2023-06-01 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| JP6655611B2 (en) | Glass cloth | |
| CN111393854A (en) | Resin composition, prepreg, laminate, and printed wiring board | |
| US20090126974A1 (en) | Manufacturing Process for a Prepreg with a Carrier, Prepreg with a Carrier, Manufacturing Process for a Thin Double-Sided Plate, Thin Double-Sided Plate and Manufacturing Process for a Multilayer-Printed Circuit Board | |
| KR101319677B1 (en) | Insulating resin composition for printed circuit board and printed circuit board comprising the same | |
| US20100078201A1 (en) | Laminated body, circuit board including laminated body, semiconductor package and process for manufacturing laminated body | |
| TWI577545B (en) | Resin composition, prepreg and metal foil-clad laminate | |
| US9894761B2 (en) | Prepreg, metal-clad laminated plate and printed wiring board | |
| US20140182903A1 (en) | Resin composition, resin varnish, prepreg, metal-clad laminate, and printed wiring board | |
| US20110009527A1 (en) | Thermosetting compositions comprising silicone polyethers, their manufacture, and uses | |
| KR20100039810A (en) | Substrate applicable in chip led package | |
| EP2692795A1 (en) | Resin composition, pre-preg, and metal foil clad laminate | |
| KR20150026557A (en) | Insulating resin composition for printed circuit board and products having the same | |
| US11584687B2 (en) | Surface-treated glass cloth | |
| CN109535628B (en) | Flame-retardant resin prepolymer, and thermosetting resin composition, prepreg and laminated board prepared from same | |
| CN115637586A (en) | Surface treatment agent, glass cloth, and prepreg | |
| JP7012505B2 (en) | Glass cloth, prepreg, and printed wiring board | |
| CN111777541B (en) | high-Tg low-dielectric active ester curing agent, preparation method and application | |
| KR102429887B1 (en) | Prepregs, laminates, printed wiring boards, coreless substrates, semiconductor packages, and methods for manufacturing coreless substrates | |
| JP2023015993A (en) | Surface treatment agent | |
| JP2002194670A (en) | Surface treating agent for glass cloth | |
| JP3291100B2 (en) | Glass fiber fabric for resin reinforcement | |
| JP4360060B2 (en) | Glass fiber fabric treated to prevent misalignment | |
| JP5493524B2 (en) | Glass cloth, prepreg manufacturing method, prepreg and laminate | |
| KR20200059296A (en) | Resin composition, prepreg, laminate and metal foil laminate | |
| JP5223660B2 (en) | Resin composition, prepreg and laminate |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination |