CN111004530A - Film composition and film formed therefrom - Google Patents

Film composition and film formed therefrom Download PDF

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Publication number
CN111004530A
CN111004530A CN201910941870.1A CN201910941870A CN111004530A CN 111004530 A CN111004530 A CN 111004530A CN 201910941870 A CN201910941870 A CN 201910941870A CN 111004530 A CN111004530 A CN 111004530A
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bismaleimide
hydrogen
film composition
film
oligomer
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朱晏颐
秦羲仪
杨伟达
官祺恩
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Industrial Technology Research Institute ITRI
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Industrial Technology Research Institute ITRI
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Priority to TW108135998A priority Critical patent/TW202014468A/en
Priority to US16/593,320 priority patent/US11059938B2/en
Publication of CN111004530A publication Critical patent/CN111004530A/en
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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D4/00—Coating compositions, e.g. paints, varnishes or lacquers, based on organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond ; Coating compositions, based on monomers of macromolecular compounds of groups C09D183/00 - C09D183/16
    • C09D4/06—Organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond in combination with a macromolecular compound other than an unsaturated polymer of groups C09D159/00 - C09D187/00

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  • Life Sciences & Earth Sciences (AREA)
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Abstract

The present disclosure provides a film composition, wherein the film composition comprises an oligomer and a crosslinker. The oligomer may have a structure of formula (I)
Figure DDA0002223131530000011
Wherein R is1And R2Independently of each other is hydrogen, C1‑20Alkyl (alkyl group), C2‑20Alkenyl group, C6‑12Aryl group, C6‑12Alkylaryl (alkylaryl group), C5‑12Cycloalkyl (cycloalkyl group), C6‑20Cycloalkylalkyl (cycloalkylalkyl group), alkoxycarbonyl (alkoxycarbonyl group), or alkylcarbonyloxy (alkylcarbonyloxy group); r1And R2Not hydrogen at the same time; a is 0 or 1; n is not less than 0; m is not less than 1, and m is not less than 1,wherein when n is not 0, the ratio of n to m is from 3:1 to 1: 4. The weight ratio of the oligomer to the crosslinker can be 9:1 to 3: 7. The oligomer has a number average molecular weight (Mn) of 1,000 to 8,000.

Description

Film composition and film formed therefrom
[ technical field ] A method for producing a semiconductor device
The present disclosure relates to a film composition and a film formed therefrom.
[ background of the invention ]
In recent years, with the development and popularization of optical communication technology, materials with lower cost and higher performance are required to prepare optical communication devices. Therefore, materials for optical communication prepared from polymer materials have attracted attention. However, when a conventional polymer material is used as a material for an optical communication device, various problems (e.g., low heat resistance, low light transmittance, or low glass transition temperature) are encountered.
In view of the above, there is a need for a novel polymer material to solve the problems encountered in the prior art.
[ summary of the invention ]
The present disclosure provides a film composition, wherein the film composition comprises an oligomer and a cross-linking agent. The oligomer (oligomer) may have a structure represented by the formula (I)
Figure BDA0002223131520000011
Wherein R is1And R2Independently of each other is hydrogen, C1-20Alkyl (alkyl group), C2-20Alkenyl group, C6-12Aryl group, C6-12Alkylaryl (alkylaryl group), C5-12Cycloalkyl (cycloalkyl group), C6-20Cycloalkylalkyl (cycloalkylalkyl group), alkoxycarbonyl (alkoxycarbonyl group), or alkylcarbonyloxy (alkylcarbonyloxy group); r1And R2Not hydrogen at the same time; a is 0 or 1; n is not less than 0; m ≧ 1, wherein when n is not 0, the ratio of n to m is 3:1 to 1:4, such as 3:1 to 1:3 or 2:1 to 1: 2. The crosslinking agent may be a compound having at least two crosslinkable functional groups, which may be C, or a bismaleimide2-5Alkenyl groups (alkenyl groups), methacrylate groups (methacrylate groups), acrylate groups (acrylate groups), acryl groups (acryl groups), epoxy groups (epoxy groups) or carboxyl groups (carboxyl groups). In addition, the weight ratio of the oligomer to the crosslinker can be 9:1 to 3:7, such as 8:2 to 3:7, 7:3 to 3:7, 6:4 to 4:6, 9:1 to 5:5, or 8:2 to 5: 5. Since the film composition has a specific repeating unit
Figure BDA0002223131520000021
And a repeating unit
Figure BDA0002223131520000022
The ratio, and the specific oligomer to crosslinker ratio, allow the film composition to have better film forming properties. Thus, the film composition can be crosslinked at room temperature to form a film without any other resin or polymer.
In addition, the present disclosure also provides a film, wherein the film is a product (i.e., cured product) obtained by curing the above-described film composition. A cured product obtained from the film composition has a low dielectric constant (Dk) and a low dissipation factor (Df). In addition, the cured product obtained from the film composition also has high light transmittance (transmittance), high refractive index (refractive index), high glass transition temperature (glass transition temperature) and high thermal stability (thermal stability).
[ detailed description ] embodiments
The present disclosure provides a film composition and a film prepared from the film composition. The film is a product obtained by curing the film composition. The film may have a low dielectric constant (Dk), a low dissipation factor (Df), a high light transmittance (transmittance), a high refractive index (refractive index), a high glass transition temperature (glass transition temperature), and a high thermal stability (thermal stability), and thus is very suitable for application to optoelectronic devices such as printed circuit boards (printed circuit boards) or optical waveguide devices (optical waveguide devices).
In accordance with embodiments of the present disclosure, the present disclosure provides a film composition. The film composition includes an oligomer and a crosslinking agent. The oligomer may have a structure of formula (I)
Figure BDA0002223131520000031
Wherein R is1And R2Independently of each other is hydrogen, C1-20Alkyl (alkyl group), C2-20Alkenyl (alkeny)l group)、C6-12Aryl group, C6-12Alkylaryl (alkylaryl group), C5-12Cycloalkyl (cycloalkyl group), C6-20Cycloalkylalkyl (cycloalkylalkyl group), alkoxycarbonyl (alkoxycarbonyl group), or alkylcarbonyloxy (alkylcarbonyloxy group); r1And R2Not hydrogen at the same time; a is 0 or 1; n is not less than 1; m ≧ 1 (e.g., 100 ≧ n ≧ 1; 100 ≧ m ≧ 1; for example, n can be 0, 1,2, 3, 4,5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, 22, 23, 24, 25, 26, 27, 28, 29, 30, 31, 32, 33, 34, 35, 36, 37, 38, 39, 40, 41, 42, 43, 44, 45, 46, 47, 48, 49, 50, 51, 52, 53, 54, 55, 56, 57, 58, 59, 60, 61, 62, 63, 64, 65, 66,67, 68, 69, 70, 71, 72, 73, 74, 75, 76, 77, 78, 79, 80, 81, 82, 83, 84, 85, 86, 87, 88, 89, 90, 91, 94, 95, 96, 97, 99, 100, 6, 3, 100, 6, 3, 9, 1,6, 9, 3, or more, 11. 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, 22, 23, 24, 25, 26, 27, 28, 29, 30, 31, 32, 33, 34, 35, 36, 37, 38, 39, 40, 41, 42, 43, 44, 45, 46, 47, 48, 49, 50, 51, 52, 53, 54, 55, 56, 57, 58, 59, 60, 61, 62, 63, 64, 65, 66,67, 68, 69, 70, 71, 72, 73, 74, 75, 76, 77, 78, 79, 80, 81, 82, 83, 84, 85, 86, 87, 88, 89, 90, 91, 92, 93, 94, 95, 96, 97, 98, 99, 100, or more than 100.
According to embodiments of the present disclosure, the oligomer may have a number average molecular weight (Mn) of 1,000 to 8,000, such as about 1,000 to 7,500, about 1,000 to 7,000, about 1,000 to 6,000, or about 1,000 to 5,000. In this way, the oligomer has good solubility in organic solvents, increasing its processability (processability). In addition, the oligomers of the present disclosure have better storability (storage) than copolymers prepared from vinyl norbornene and norbornene alone. According to an embodiment of the present disclosure, the repeating unit
Figure BDA0002223131520000041
And the repeating unit
Figure BDA0002223131520000042
Repeating in a random manner or in a block manner. If the number average molecular weight of the oligomer is too high, the processability of the cured product of the obtained film composition is poor; if the number average molecular weight of the oligomer is too low, the heat resistance of the cured product of the obtained film composition is poor.
For example, R1And R2And may independently be a linear or branched (linear or branched) alkyl group, wherein the alkyl group may have 1,2, 3, 4,5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, or 20 carbon atoms. According to the embodiments of the present disclosure, the alkenyl group of the present disclosure may be a linear or branched alkenyl group. For example, R1And R2And may independently be a straight or branched alkenyl group, wherein the alkenyl group may have 2, 3, 4,5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, or 20 carbon atoms.
According to an embodiment of the disclosure, R1And R2Can independently be hydrogen, or
Figure BDA0002223131520000043
Wherein b can be 0, 1,2, 3, 4,5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, or 19; and, R1And R2Not hydrogen at the same time. According to an embodiment of the disclosure, C of the disclosure6-12The aryl group may be phenyl, biphenyl, or naphthyl.
According to an embodiment of the disclosure, R1And R2Independently of one another is hydrogen, or
Figure BDA0002223131520000044
Wherein c can be 0, 1,2, 3, 4,5, or 6; and, R1And R2Not hydrogen at the same time.
In accordance with the present disclosureExample, R1And R2 can independently be hydrogen, or
Figure BDA0002223131520000045
Wherein d can be 0, 1,2, 3, 4,5, or 6; and, R1And R2Not hydrogen at the same time.
According to an embodiment of the disclosure, R1And R2Can independently be hydrogen, or
Figure BDA0002223131520000051
Wherein e can be 0, 1,2, 3, 4,5, or 6; and, R1And R2Not hydrogen at the same time.
According to an embodiment of the disclosure, R1And R2Can independently be hydrogen, or
Figure BDA0002223131520000052
Wherein f can be 0, 1,2, 3, 4,5, or 6, R3Can be C1-6Alkyl (alkyl group), R1And R2Not hydrogen at the same time. For example, R3May be methyl (methyl group), ethyl (ethyl group), propyl (propyl group) (e.g. n-propyl (n-propyl group), or isopropyl (isopropyl group)), butyl (butyl group) (e.g. n-butyl (n-butyl group), sec-butyl (s-butyl group), isobutyl (isobutyl group), or tert-butyl (tert-butyl group)), pentyl (pentyl group), or hexyl (hexyl group).
According to an embodiment of the disclosure, R1And R2Can independently be hydrogen, or
Figure BDA0002223131520000053
Wherein g can be 0, 1,2, 3, 4,5, or 6, R4Can be C1-6An alkyl group; and, R1And R2Not hydrogen at the same time. For example, R4Can be methyl (methyl group), ethyl (ethyl group), propyl (propyl group) (e.g. n-propyl group, or isopropyl group), butyl (butyl group) (e.g. n-butyl group, s-butyl group, isobutyl (isobutyl group), or tert-butyl (tert-butyl group)) Pentyl (pentyl), or hexyl (hexyl).
According to an embodiment of the disclosure, R1And R2Can independently be hydrogen, or
Figure BDA0002223131520000054
Wherein h can be 1,2, 3, 4,5, or 6; and, R1And R2Not hydrogen at the same time.
According to an embodiment of the disclosure, R1And R2Can independently be hydrogen, or
Figure BDA0002223131520000055
Wherein i can be 0, 1,2, 3, 4,5, or 6; and, R1And R2Not hydrogen at the same time.
According to an embodiment of the disclosure, R1And R2Can independently be hydrogen, or
Figure BDA0002223131520000061
Wherein j can be 0, 1,2, 3, 4,5, or 6; and, R1And R2Not hydrogen at the same time.
The ratio of n to m can be 3:1 to 1:4, for example about 3:1 to 1:3, about 2:1 to 1:2, or about 1: 1. When the ratio of n to m is too high or too low, it results in poor film-forming properties of the film composition having the oligomer, and thus, the film composition cannot form a film after being cured.
According to an embodiment of the present disclosure, the oligomer may be uniformly dispersed in the cross-linking agent. As such, the film compositions of the present disclosure may include a solvent. According to an embodiment of the present disclosure, the film composition of the present disclosure may further include a solvent for dissolving the oligomer and the crosslinking agent. Therefore, the oligomer and the crosslinking agent can be uniformly dispersed in the solvent. According to embodiments of the present disclosure, the solvent may have a weight percentage of about 1 wt% to 500 wt%, based on the weight of the oligomer and the crosslinking agent. The solvent may be an aromatic hydrocarbon solvent, an alcohol solvent, an ether solvent, a ketone solvent, an ester solvent, a nitrogen-containing solvent, or a combination thereof. For example, the solvent may be benzene (toluene), toluene (toluene), xylene (xylene), mesitylene (mesitylene), methanol (methyl alcohol), ethanol (ethyl alcohol), butanol (butanol), ethyl cellosolve (ethyl cellolose), butyl cellosolve (butyl cellosolve), ethylene glycol monomethyl ether (ethylene glycol monomethyl ether), carbitol (carbitol), butyl carbitol (butyl carbitol), acetone (acetone), methyl ethyl ketone (methyl ethyl ketone), methyl isobutyl ketone (methyl isobutylketone), cyclohexanone (cyclohexanone), ethyl methoxyacetate (methyl methoxyacetate), ethyl ethoxyacetate (ethylene xyacetate), ethyl butoxyacetate (butyl methoxyacetate), ethyl acetate (ethyl acetate), ethyl acetate (propylene glycol), propylene glycol (propylene glycol) acetate (methyl pyrrolidone, N-dimethyl formamide (2-methyl pyrrolidone), N-methyl pyrrolidone (2-methyl pyrrolidone), N-methyl pyrrolidone (N-methyl pyrrolidone ), N-methyl pyrrolidone (N-methyl pyrrolidone, N-methyl pyrrolidone (N-methyl pyrrolidone), N-methyl pyrrolidone (N-methyl pyrrolidone), N-methyl pyrrolidone (N-methyl pyrrolidone), N-methyl pyrrolidone, N-methyl, Or combinations of the foregoing
According to an embodiment of the present disclosure, the film composition further comprises an additive, wherein the additive may be an initiator, a leveling agent, a filler, a colorant, a defoamer, a flame retardant, or a combination thereof. According to embodiments of the present disclosure, the additive may have a weight percentage of about 1 wt% to 50 wt%, based on the weight of the oligomer and the crosslinker.
According to the disclosed embodiments, the film composition may be composed of an oligomer and a cross-linking agent. According to embodiments of the present disclosure, the film composition consists essentially of a solvent, an oligomer, and a crosslinker.
The crosslinking agent can be a compound having at least two crosslinkable functional groups (e.g., a compound having two crosslinkable functional groups, a compound having three crosslinkable functional groups, a compound having four crosslinkable functional groups, or a compound having five crosslinkable functional groups) or a bismaleimide, where the crosslinkable functional group can be C2-5Alkenyl groups (e.g. vinyl, allyl, butyl)An alkenyl group (1, 3-butadienyl group), a 1-methylvinyl group (1-methyl vinyl group), a 1-methallyl group (1-methallyl group), a1, 1-dimethylallyl group (1, 1-dimethylallyl group), a 2-methallyl group (2-methallyl group), or a1, 2-dimethylallyl group (1, 2-dimethylallyl group), a methacrylate group (methacrylate group), an acrylate group (acrylate group), an acryloyl group (acrylate group), an epoxy group (epoxy group), a carboxyl group (carboxyl group), or a combination thereof.
According to embodiments of the present disclosure, the crosslinking agent can have a number average molecular weight (Mn) of less than or equal to 600, such as about 50 to 550, about 60 to 550, about 70 to 550, about 80 to 500, or about 90 to 500.
According to embodiments of the present disclosure, the crosslinking agent may comprise a methacrylate-type agent, such as: SR 205H: triethylene glycol dimethacrylate (TiEGDMA); SR 206H: ethylene Glycol Dimethacrylate (EGDMA); SR 209: tetraethyleneglycol dimethacrylate (TTEGDMA); SR210 HH: polyethylene glycol (200) dimethacrylate (PEG 200DMA), SR 214: 1,4-butanediol dimethacrylate (1, 4-butylene glycol dimethacrylate, BDDMA), SR 231: diethylene glycol dimethacrylate (DEGDMA), SR 239: 1,6-hexanediol dimethacrylate (1,6-hexanediol dimethacrylate, HDDMA), SR 252: polyethylene glycol (600) dimethacrylate, BPA 600DMA), SR 262: 1,12-dodecanediol dimethacrylate (1,12-dodecanediol dimethacrylate, DDDDDDMA), SR 297J: 1, 3-butanediol dimethacrylate (1,3-butylene glycol dimethacrylate, BGB 63348: bisphenol A3, bisphenol A3 dimethacrylate (bisphenol A3, bisphenol A3-ethylene dimethacrylate (2, 3-diethylene glycol dimethacrylate, BDMA), BPA2 EODMA); SR 350D: trimethylolpropane trimethacrylate (TMPTMA); SR 480: ethoxylated 10bisphenol a dimethacrylate (ethoxylated 10bisphenol a dimethacrylate, BPA10 EODMA); SR 540: ethoxylated 4bisphenol a dimethacrylate (ethoxylated 4bisphenol acrylate, BPA4 EODMA); SR 596: alkoxylated pentaerythritol tetra methacrylate (PETTMA); SR 604: polypropylene Glycol Monomethacrylate (PPGMA); and SR 834: tricyclodecane dimethanol dimethacrylate (TCDDMDMA).
According to embodiments of the present disclosure, the crosslinking agent may comprise acrylate-type reagents, such as: dipentaerythritol hexaacrylate (DPHA); SR 238: 1,6-hexanediol diacrylate (1,6-hexanediol diacrylate, HDDA); SR 259: polyethylene glycol (200) diacrylate (PEG 200 diacrylate, PEG200 DA); SR 268G: tetraethyleneglycol diacrylate (TTEGDA); SR 272: triethylene glycol diacrylate (TIEGDA); SR 295: pentaerythritol tetraacrylate (PETTA); SR 306: tripropylene glycol diacrylate (TPGDA); SR 307: polybutadiene diacrylate (PBDDA); SR 341: 3-methyl 1,5-pentanediol diacrylate (3-methyl 1, 5-pentanedionate, MPDA); SR 344: polyethylene glycol (400) diacrylate (PEG 400 diacrylate, PEG400 DA); SR 349: ethoxylated 3bisphenol a diacrylate (ethoxylated 3bisphenol a diacrylate, BPA3 EODA); SR 351: trimethylolpropane triacrylate (TMPTA); SR 355: di-trimethylolpropane tetraacrylate (Di-trimethyolpropane tetraacrylate, Di-TMPTTA); SR 368: tris (2-hydroxyethyl) isocyanurate triacrylate ((tris (2-hydroxyethyl) isocyanurate triacrylate, THEICATA), SR 399: dipentaerythritol pentaacrylate (DPPA), SR 415: ethoxylated (20) trimethylolpropane triacrylate (ethoxylated (20) trimethylolpropane triacrylate, TMP20 TA), SR 444D: pentaerythritol triacrylate (pentaerythrityl triacrylate, PETIA), SR 454: ethoxylated 3trimethylolpropane triacrylate (ethoxylated 3trimethylolpropane triacrylate, TMP3EOTA), SR 492: propoxylated3trimethylolpropane triacrylate (propoxylated3trimethylolpropane triacrylate, TMP3POTA 494; ethoxylated 4 pentaerythritol tetraacrylate (trimethylolpropane triacrylate, TMP6, SR 508: trimethylolpropane triacrylate; trimethylolpropane ethoxylate, TMP6, SR 508: trimethylolpropane triacrylate, TMP6, DPGDA); SR 595: 1,10decanediol diacrylate (1,10 decanodiol diacrylate, DDDA); SR 601E: ethoxylated 4bisphenol A diacrylate ((ethoxylated 4bisphenol A diacrylate, BPA4 EODA); SR 602: ethoxylated 10bisphenol A diacrylate (BPA 10E0 DA); SR 606A: esterdiol diacrylate (EDDA); SR 610: polyethylene glycol (600) diacrylate (PEG 600 DA); SR 802: alkoxylated diacrylate (alkoxylated diacrylate) SR 833S: tricyclodecane dimethanol diacrylate (tricyclohededipropyl methacrylate, TCDDMDA); SR 9003: propoxylated 2neopentyl glycol diacrylate (propoxylated 2 glycidyl diacrylate) (PONPA); SR 20: glycerol 903 (propoxylated 3: EOpropyl methacrylate, TPA 5: trimethylolpropane triacrylate) (SR 15: ethoxylated glycerol methacrylate, SR 12: ethoxylated trimethylolpropane triacrylate) (SR 15: TMP 12); SR 15: ethoxylated glycerol triacrylate SR 12).
According to embodiments of the present disclosure, the crosslinking agent may comprise an allylic type reagent, such as: triallyl cyanurate (TAC); triallyl isocyanurate (TAIC); triallyl phosphate (TAP); triallyl borate (TAB); trimethylallyl isocyanurate (TMAIC); diallyl terephthalate (DATP); diallyl carbonate (diallyl carbonate); diallyl maleate (diallyl maleate); diallyl fumarate (diallyl fumarate);
diallyl phosphite (diallyl phosphite); trimethylolpropane diallyl ether (trimethylpropane diallyl ether); and tetraallyloxyethane (1,1,2, 2-tetraallyloxyethane).
According to embodiments of the present disclosure, the crosslinking agent may comprise a vinyl type (vinylic type) agent, such as: bis (vinylphenyl) ethane (BVPE); bis (4-vinylphenyl) methane (Bis (4-vinylphenyl) methane); 1,4-butadiene (1, 4-butadiene); divinylacetylene (divinylacetylene); divinylbenzene (DVB); divinyl ethers (divinyl ethers); divinyl sulfide (divinyl sulfide); divinyl sulfone (divinyl sulfone); divinyl sulfoxide (divinyl sulfoxide); 1, 3-divinylcyclohexane (l, 3-divinylcyclohexylcyclohexane); 1,3-divinylcyclopentane (1, 3-divinylcyclopentane); 1,5-hexadiene (1, 5-hexadiene); isoprene (isoprene); and 1,2,4-trivinylcyclohexane (1,2,4-trivinyl cyclohexane, TVCH).
According to embodiments of the present disclosure, the crosslinker may comprise a hybrid (hybird type) reagent, such as: allyl methacrylate (allyl methacrylate); and allyl acrylate.
According to embodiments of the present disclosure, the crosslinker may comprise bismaleimide. The bismaleimide has a structure shown in a formula (II) or a formula (III)
Figure BDA0002223131520000101
Figure BDA0002223131520000102
Wherein R is5May be-CR2-、-NR-、-C(O)CH2-、-CH2OCH2-、-C(O)-、-O-、-O-O-、-S-、-S-S-、-S(O)-、-CH2S(O)CH2-、-(O)S(O)-、-C6R4-、-CH2(C6R4)CH2-、-CH2(C6R4) (O) -, substituted or unsubstituted biphenylene (diphenylene), R6is-CR2-, - -C (O) - -, - -O- -, - -S- -, - - (O) S (O) - -, or- -S (O) - -; and R is independently hydrogen or C1-4An alkyl group. Wherein (O) in the above-mentioned group structure represents an oxygen atom bonded to C or S in the form of a double bond. Wherein substituted biphenylene refers to a divalent aromatic radical having at least one carbon hydrogen replaced by C1-6Alkyl groups are substituted. The bismaleimide can be N, N '-bismaleimide-4, 4' -diphenylmethane (N, N '-bismalemide-4, 4' -diphenylmethane), 1 '- (methylenebis-4, 1-phenylene) bismaleimide (1, 1' - (methylene-4, 1-phenylene) bismaleimide), N '- (1, 1' -biphenyl-4,4 '-diyl) bismaleimide (N, N' - (1,1 '-bipheny 1-4, 4' -diyl) bismaleimide), N '- (4-methyl-1,3-phenylene) bismaleimide (N, N' - (4-methyl-1,3-phenylene) bismaleimide), 1 '- (3, 3' -dimethyl-1, 1 '-biphenyl-4, 4' -diyl) bismaleimide (1,1 '- (3, 3' -dimethyl-1, 1 '-biphenyl-4, 4' -diyl) bismaleimide), N, N '-ethylenebismaleimide (N, N' -ethylenebismaleimide), N, N '- (1,2-phenylene) bismaleimide (N, N' - (1,2-phenylene) bismaleimide), N, N '- (1,3-phenylene) bismaleimide (N, N' - (1,3-phenylene) bismaleimide), N, N '-bismaleimide sulfide (N, N' -thiobismaleimide), N, N '-bismaleimide disulfide (N, N' -thiobismaleimide), N, N '-bismaleimide ketone (N, N' -ketinediimide), N, N '-methylenebismaleimide (N, N' -methylene-bis-maleinimide), bismaleimide methyl-ether (bis-maleinimidopropyl-ether), 1, 2-bismaleimide-1, 2-ethanediol (1,2-bis- (maleimido) -1, 2-ethanediol), N '-4, 4' -diphenylether-bismaleimide (N, N '-4, 4' -diphenyleneimide-bis-maleimid), 4 '-bismaleimide-diphenyl sulfone (4, 4' -bis- (maleimido) -diphenylsulfone), or a combination thereof.
According to embodiments of the disclosure, the weight ratio of the oligomer to the crosslinker can be 9:1 to 3:7, such as about 8:2 to 2:8, about 7:3 to 3:7, about 6:4 to 4:6, about 9:1 to 5:5, or about 8:2 to 5: 5. For example, the ratio of the oligomer to the crosslinker can be about 9:1, 8:2, 7:3, 6:4, 5:5, 4:6, or 3: 7. Since the film composition has a specific oligomer to crosslinker ratio, the film composition has better film forming properties.
According to an embodiment of the present disclosure, the film composition does not include a resin component. Wherein the resin comprises a polyolefin resin (e.g., a polybutadiene resin (polybutadiene resin), a polycycloolefin resin (polycycloolefin resin), a cyclic olefin polymer resin (cycloolefine polymer resin), or a cyclic olefin copolymer resin (cycloolefine copolymer resin), an epoxy resin (epoxyresin), a cyanurate resin (cyclocyanurate resin), a polystyrene resin (polystyrene resin), a polybenzoxazole resin (polybenzoxazole resin), a polybenzcyclobutene resin (polybenzoxazole resin), a polyaryletherether resin (polyaryleneether resin), a polysiloxane resin (polysiloxazene resin), a polyester resin (polyester resin), a styrene butadiene copolymer resin (polystyrene-polybutadiene resin), a polyimide resin (polyimide resin), a maleimide resin (polyphenylene resin), a polyphenylene ether resin (polyphenylene ether resin), or a combination thereof.
The resulting cured product of the film composition has a refractive index (refractivity index) of about 1.3001 to 0.8999, and a glass transition temperature (glass transition temperature) of about 140 ℃ to 300 ℃. In addition, the present disclosure also provides a cured product of the film composition. According to embodiments of the present disclosure, the thin film composition of the present disclosure may be crosslinked at a temperature of less than 250 ℃ (e.g., about 60 ℃ to 200 ℃, about 80 ℃ to 180 ℃, about 100 ℃ to 150 ℃, or about 120 ℃ to 140 ℃) to obtain the cured product.
In order to make the aforementioned and other objects, features, and advantages of the present disclosure more comprehensible, several embodiments accompanied with figures are described in detail below:
preparation of oligomers
Preparation example 1:
0.09 g of 1,3-bis (2,4,6-trimethylphenyl) -4,5-dihydroimidazol-2-yl [2- (isopropoxy-5- (N, N-dimethylaminosulfonyl) phenyl ] are added]Methyl ruthenium dichloride (1,3-Bis (2,4, 6-trimethyonyl) -4, 5-dihydrazod-2-ylidine [2- (i-methoxy) -5- (N, N-dimethylaminosulfonyl) phenyl]methylene (ii) dichloride (as a metal catalyst) was added to a first reaction flask under nitrogen, and 15 ml of toluene was added to the first reaction flask to obtain a metal catalyst solution. After the metal catalyst was completely dissolved in toluene, 1-hexene (0.483mol), 98.4 g of Vinylnorbornene (VNB) and 170 ml of toluene were added to the second reaction flask. Next, the metal catalyst solution in the first reaction vessel was added to the second reaction vessel. After stirring well, a norbornene solution (153.8 g of Norbornene (NB) in 190 ml of toluene) was added to the second reaction flask. Here, the molar percentage of 1-hexene was 20 mol% based on the total molar number of vinylnorbornene and norbornene. After the reaction was complete, 130 ml of ethyl vinyl ether (ethyl vinyl ether) was added to the second reaction flask. After stirring overnight, the resulting solution was freed of the catalyst and reprecipitated in methanol. After reconcentration, oligomer (I) having a number average molecular weight (Mn) of about 2,048, wherein the repeating units of oligomer (I) were obtained
Figure BDA0002223131520000121
And a repeating unit
Figure BDA0002223131520000122
In a ratio of about 2: 1.
Preparation example 2:
0.045 g of 1,3-bis (2,4,6-trimethylphenyl) -4,5-dihydroimidazol-2-yl [2- (isopropoxy-5- (N, N-dimethylaminosulfonyl) phenyl ] was added]Methyl ruthenium dichloride (as a metal catalyst) was added to the first reaction vessel under nitrogen, and 10ml of toluene was added to the first reaction vessel to obtain a metal catalyst solution. After the metal catalyst was completely dissolved in toluene, 1-hexene (0.604mol), 73.6 g of vinyl norbornene (vinyl) were added to the second reaction flasknorbomene, VNB), and 128 ml of toluene. Next, the metal catalyst solution in the first reaction vessel was added to the second reaction vessel. After stirring well, a norbornene solution (57.7 g of Norbornene (NB) in 50 ml of toluene) was added to the second reaction flask. Here, the molar percentage of 1-hexene was 50 mol% based on the total molar number of vinylnorbornene and norbornene. After the reaction was complete, 63 ml of ethyl vinyl ether was added to the second reaction flask. After stirring overnight, the resulting solution was freed of the catalyst and reprecipitated in methanol. After reconcentration, oligomer (II) was obtained (having a number average molecular weight of about 1,033), wherein the repeat units of oligomer (II)
Figure BDA0002223131520000131
And a repeating unit
Figure BDA0002223131520000132
In a ratio of about 1: 1.
Preparation example 3:
0.18 g of 1,3-bis (2,4,6-trimethylphenyl) -4,5-dihydroimidazol-2-yl [2- (isopropoxy-5- (N, N-dimethylaminosulfonyl) phenyl ] are reacted]Methyl ruthenium dichloride (as a metal catalyst) was added to the first reaction vessel under nitrogen, and 30ml of toluene was added to the first reaction vessel to obtain a metal catalyst solution. After the metal catalyst was completely dissolved in toluene, 1-hexene (0.967mol), 392.7 g of Vinylnorbornene (VNB) and 620ml of toluene were added to the second reaction flask. Next, the metal catalyst solution in the first reaction vessel was added to the second reaction vessel. After stirring well, a norbornene solution (153.7 g of Norbornene (NB) dissolved in 100 ml of toluene) was added to the second reaction flask. Here, the molar percentage of 1-hexene was 20 mol% based on the total molar number of vinylnorbornene and norbornene. After the reaction was complete, 250 ml of ethyl vinyl ether was added to the second reaction flask. After stirring overnight, the resulting solution was freed of the catalyst and reprecipitated in methanol. After reconcentration, oligomer (III) (having a number average molecular weight of about 2,065) was obtained, wherein the oligomer (I)II) recurring units
Figure BDA0002223131520000133
And a repeating unit
Figure BDA0002223131520000134
In a ratio of about 1: 2.
Preparation example 4:
0.054 g of 1,3-bis (2,4,6-trimethylphenyl) -4,5-dihydroimidazol-2-yl [2- (isopropoxy-5- (N, N-dimethylaminosulfonyl) phenyl ] are reacted]Methyl ruthenium dichloride (as a metal catalyst) was added to the first reaction vessel under nitrogen, and 10ml of toluene was added to the first reaction vessel to obtain a metal catalyst solution. After the metal catalyst was completely dissolved in toluene, 1-hexene (0.291mol), 35.3 g of Vinylnorbornene (VNB), and 65 ml of toluene were added to the second reaction flask. Next, the metal catalyst solution in the first reaction vessel was added to the second reaction vessel. After stirring well, a norbornene solution (110.8 g of Norbornene (NB) dissolved in 150 ml of toluene) was added to the second reaction flask. Here, the molar percentage of 1-hexene was 20 mol% based on the total molar number of vinylnorbornene and norbornene. After the reaction was complete, 75 ml of ethyl vinyl ether was added to the second reaction flask. After stirring overnight, the resulting solution was freed of the catalyst and reprecipitated in methanol. After reconcentration, oligomer (IV) is obtained (having a number average molecular weight of about 1,880), wherein the repeat units of oligomer (IV)
Figure BDA0002223131520000141
And a repeating unit
Figure BDA0002223131520000142
In a ratio of about 4: 1.
Preparation example 5:
0.054 g of 1,3-bis (2,4,6-trimethylphenyl) -4,5-dihydroimidazol-2-yl [2- (isopropoxy-5- (N, N-dimethylaminosulfonyl) phenyl ] are reacted]Methyl ruthenium dichloride (as metal catalyst) was added under nitrogen to a first reaction flask and 10ml of toluene was added in the first reactionIn a bottle, a metal catalyst solution was obtained. After the metal catalyst was completely dissolved in toluene, 1-hexene (0.735mol), 147.4 g of Vinylnorbornene (VNB), and 180ml of toluene were added to the second reaction flask. Next, the metal catalyst solution in the first reaction vessel was added to the second reaction vessel. After stirring well, a norbornene solution (23.06 g of Norbornene (NB) in 35 ml of toluene) was added to the second reaction flask. Here, the molar percentage of 1-hexene was 50 mol% based on the total molar number of vinylnorbornene and norbornene. After the reaction was complete, 75 ml of ethyl vinyl ether was added to the second reaction flask. After stirring overnight, the resulting solution was freed of the catalyst and reprecipitated in methanol. After reconcentration, oligomer (V) (having a number average molecular weight of about 1,254) was obtained in which the repeating units of the oligomer (V)
Figure BDA0002223131520000143
And a repeating unit
Figure BDA0002223131520000144
In a ratio of about 1: 5.
Preparation example 6:
0.054 g of 1,3-bis (2,4,6-trimethylphenyl) -4,5-dihydroimidazol-2-yl [2- (isopropoxy-5- (N, N-dimethylaminosulfonyl) phenyl ] are reacted]Methyl ruthenium dichloride (as a metal catalyst) was added to the first reaction vessel under nitrogen, and 10ml of toluene was added to the first reaction vessel to obtain a metal catalyst solution. After the metal catalyst was completely dissolved in toluene, 1-hexene (0.435mol), 44.2 g of Vinylnorbornene (VNB) and 80ml of toluene were added to the second reaction flask. Next, the metal catalyst solution in the first reaction vessel was added to the second reaction vessel. After stirring well, a norbornene solution (103.5 g of Norbornene (NB) in 135 ml of toluene) was added to the second reaction flask. Here, the molar percentage of 1-hexene was 30 mol% based on the total molar number of vinylnorbornene and norbornene. After the reaction was complete, 75 ml of ethyl vinyl ether was added to the second reaction flask. Stirring overnight and removing the resulting solutionThe catalyst was reprecipitated in methanol. After reconcentration, oligomer (VI) was obtained (having a number average molecular weight of about 1,746), wherein the repeat units of oligomer (VI)
Figure BDA0002223131520000151
And a repeating unit
Figure BDA0002223131520000152
In a ratio of about 3: 1.
Preparation example 7
0.054 g of 1,3-bis (2,4,6-trimethylphenyl) -4,5-dihydroimidazol-2-yl [2- (isopropoxy-5- (N, N-dimethylaminosulfonyl) phenyl ] are reacted]Methyl ruthenium dichloride (as a metal catalyst) was added to the first reaction vessel under nitrogen, and 10ml of toluene (tolumen) was added to the first reaction vessel to obtain a metal catalyst solution. After the metal catalyst was completely dissolved in toluene, 1-hexene (0.044mol), 141.3 g of Vinylnorbornene (VNB) and 180ml of toluene were added to the second reaction flask. Next, the metal catalyst solution in the first reaction vessel was added to the second reaction vessel. After stirring well, a norbornene solution (27.81 g of Norbornene (NB) in 35 ml of toluene) was added to the second reaction flask. Here, the mole percent ratio of 1-hexene was 3 mol% based on the total number of moles of vinylnorbornene and norbornene. After the reaction was complete, 75 ml of ethyl vinyl ether was added to the second reaction flask. After stirring overnight, the resulting solution was freed of the catalyst and reprecipitated in methanol. After reconcentration, oligomer (VII) was obtained (having a number average molecular weight of about 7,539), wherein the repeat units of the oligomer (VII)
Figure BDA0002223131520000161
And a repeating unit
Figure BDA0002223131520000162
In a ratio of about 1: 4.
Preparation example 8
0.0018 g of 1,3-bis (2,4,6-trimethylphenyl) -4,5-dihydroimidazol-2-yl [2- (isopropoxy-5- (N, N-dimethylamine)Sulfonyl) phenyl]Methyl ruthenium dichloride (as a metal catalyst) was added to the first reaction vessel under nitrogen, and 0.5 ml of toluene (toluene) was added to the first reaction vessel to obtain a metal catalyst solution. After the metal catalyst was completely dissolved in toluene, 0.043mol of methyl acrylate (methyl acrylate), 3g of Vinylnorbornene (VNB), and 4.5 ml of toluene were added to the second reaction flask. Next, the metal catalyst solution in the first reaction vessel was added to the second reaction vessel. After stirring well, a norbornene solution (2.36 g of Norbornene (NB) in 5 ml of toluene) was added to the second reaction flask. Here, the molar percentage of methyl acrylate was 85 mol%, based on the total molar number of vinyl norbornene and norbornene. After the reaction was complete, 2.5 ml of ethyl vinyl ether (ethyl vinyl ether) was added to the second reaction flask. After stirring overnight, the resulting solution was freed of the catalyst and reprecipitated in methanol. After reconcentration, the oligomer (VIII) (having a number average molecular weight of about 3,699) is obtained in which the repeat units of the oligomer (VIII)
Figure BDA0002223131520000163
And a repeating unit
Figure BDA0002223131520000164
In a ratio of about 1: 1. R1And R2Can independently be hydrogen, or
Figure BDA0002223131520000165
Wherein f is 0, R3Is C1Alkyl (alkyl group), R1And R2Not hydrogen at the same time.
Preparation example 9
0.018 g of 1,3-bis (2,4,6-trimethylphenyl) -4,5-dihydroimidazol-2-yl [2- (isopropoxy-5- (N, N-dimethylaminosulfonyl) phenyl ] was added]Methyl ruthenium dichloride (as a metal catalyst) was added to the first reaction vessel under nitrogen, and 10ml of toluene (toluene) was added to the first reaction vessel to obtain a metal catalyst solution. After the metal catalyst was completely dissolved in toluene, 0.247mol of 1-octadecene (1-o) was added to the second reaction flaskctadecene), 29.4 g of Vinylnorbornene (VNB), and 45 ml of toluene. Next, the metal catalyst solution in the first reaction vessel was added to the second reaction vessel. After stirring well, a norbornene solution (23.06 g of Norbornene (NB) in 20ml of toluene) was added to the second reaction flask. Here, the molar percentage of 1-octadecene was 50 mol% based on the total molar number of vinyl norbornene and norbornene. After the reaction was complete, 25 ml of ethyl vinyl ether (ethyl vinyl ether) was added to the second reaction flask. After stirring overnight, the resulting solution was freed of the catalyst and reprecipitated in methanol. After reconcentration, oligomer (IX) (having a number average molecular weight of about 871) was obtained in which the repeating units of the oligomer (IX)
Figure BDA0002223131520000171
And a repeating unit
Figure BDA0002223131520000172
In a ratio of about 1: 1.
Preparation example 10
The procedure was carried out in the same manner as described in preparation example 9, except that 1-octadecene (1-octadecene) was replaced with styrene (styrene), to obtain oligomer (X) (having a number average molecular weight of about 1,936).
Preparation example 11
The procedure was carried out as described in preparation 9, except that 1-octadecene (1-octadecene) was replaced with 1,5-hexadiene (1,5-hexadiene) to give oligomer (XI) (having a number average molecular weight of about 1,072).
Preparation example 12
0.006 g of 1,3-bis (2,4,6-trimethylphenyl) -4,5-dihydroimidazol-2-yl [2- (isopropoxy-5- (N, N-dimethylaminosulfonyl) phenyl ] was added]Methyl ruthenium dichloride (as a metal catalyst) was added to the first reaction flask under nitrogen, and 4 ml of toluene (toluene) was added to the first reaction flask to obtain a metal catalyst solution. After the metal catalyst was completely dissolved in toluene, 0.008mol of 1-vinylcyclohexane (vinylcyclohexane), 9.8 g of Vinylnorbornene (VNB) and 15 ml of toluene were added to the second reaction flask. Then, the above-mentioned steps are mixedThe metal catalyst solution in the first reaction flask is added into the second reaction flask. After stirring well, a norbornene solution (7.69 g of Norbornene (NB) in 7 ml of toluene) was added to the second reaction flask. Here, the mole percent ratio of 1-vinylcyclohexane is 5 mol%, based on the total number of moles of vinylnorbornene and norbornene. After the reaction was complete, 8 ml of ethyl vinyl ether (ethyl vinyl ether) was added to the second reaction flask. After stirring overnight, the resulting solution was freed of the catalyst and reprecipitated in methanol. After reconcentration, an oligomer (XII) having a number average molecular weight of about 1,988 is obtained in which the repeat units of the oligomer (XII)
Figure BDA0002223131520000181
And a repeating unit
Figure BDA0002223131520000182
In a ratio of about 1: 1. R1And R2At least one may be
Figure BDA0002223131520000183
The remainder being hydrogen, wherein d is 0.
Preparation example 13
The procedure was carried out in the same manner as described in preparation 9, except that 1-octadecene (1-octadecene) was replaced with allyl acetate (allyl acetate), to give oligomer (XIII) (having a number average molecular weight of about 2,779). R1And R2At least one is
Figure BDA0002223131520000184
The remainder being hydrogen, wherein g is 1, R4Is CH3。
Preparation example 14
The procedure was carried out as described in preparation 9, except that 1-octadecene (1-octadecene) was reduced from 0.247mol to 0.049mol, giving oligomer (XIV) (having a number average molecular weight of about 2,736).
The thermal cracking temperature (Td) (1% weight loss) of the oligomer (II) and the oligomer (IX) was measured, and the results are shown in Table 1.
Oligomer (II) Oligomer (IX)
Number average molecular weight 1033 871
Temperature of thermal cracking (. degree.C.) 110℃ 75℃
As is clear from Table 1, the oligomer (IX) having a number average molecular weight of less than 1,000 may have a low thermal cracking temperature, which may result in poor heat resistance of the cured product of the resulting film composition.
Preparation example 15
0.054 g of 1,3-bis (2,4,6-trimethylphenyl) -4,5-dihydroimidazol-2-yl [2- (isopropoxy-5- (N, N-dimethylaminosulfonyl) phenyl ] are reacted]Methyl ruthenium dichloride (as a metal catalyst) was added under nitrogen to a first reaction flask and 30ml of toluene (tolumen) was added to the first reaction flask to obtain a metal catalyst solution, after the metal catalyst was completely dissolved in toluene, 0.725mol of 1-hexene (α -olefin), 177 g of Vinylnorbornene (VNB), and 300 ml of toluene were added to a second reaction flask, and then the metal catalyst solution in the first reaction flask was added to the second reaction flask, where the molar percentage of α -olefin (1-hexene) was 50 mol% based on the molar of vinylnorbornene, after completion of the reaction, 75 ml of ethyl vinyl ether (ethyl vinyl ether) was added to the second reaction flask, and stirred overnightThe resulting solution was then freed of the catalyst and reprecipitated in methanol. After reconcentration, a copolymer (XV) was obtained (having a number average molecular weight of about 1,225) in which the recurring units of the copolymer (XV) were all
Figure BDA0002223131520000191
Film composition
Comparative example 1
Oligomer (I) (100 parts by weight) and initiator (1 part by weight,
Figure BDA0002223131520000192
was charged into a reaction flask, and xylene was added to dissolve (20 parts by weight). After stirring uniformly, a film composition was obtained. Next, the film composition was coated on a copper foil (manufactured and sold by guhe electric industry co., ltd.). Subsequently, the copper foil was gradually heated to 230 ℃. However, since the film composition does not include a crosslinking agent, a crosslinking reaction may not proceed, and thus a film may not be obtained after the film composition is subjected to a heat curing process.
Example 1
Oligomer (I) (90 parts by weight), triallyl isocyanurate (10 parts by weight), and an initiator (1 part by weight,
Figure BDA0002223131520000193
was charged into a reaction flask, and xylene was added to dissolve (30 parts by weight). After stirring uniformly, a film composition was obtained. Next, the film composition was coated on a copper foil (manufactured and sold by guhe electric industry co., ltd.). Then, the copper foil is gradually heated to perform a crosslinking reaction on the film composition at 230 ℃ to obtain a film layer. The refractive index of the film was measured by a reflection film thickness meter (reflectometer), and the glass transition temperature of the film was measured by a Differential Scanning Calorimeter (DSC), and the results are shown in table 2.
Example 2
The procedure was carried out as described in example 1, except that the ratio of oligomer (I) to triallylisocyanurate was adjusted from 9:1 to 8:2, to give a film composition. Next, the film composition was coated on a copper foil (manufactured and sold by guhe electric industry co., ltd.). Then, the copper foil is gradually heated to perform a crosslinking reaction on the film composition at 230 ℃ to obtain a film layer. Next, the refractive index of the film was measured by a reflection type film thickness measuring instrument, and the glass transition temperature of the film was measured by a differential scanning calorimeter, and the results are shown in table 2.
Example 3
The procedure was carried out as described in example 1, except that the ratio of oligomer (I) to triallylisocyanurate was adjusted from 9:1 to 5:5, to obtain a film composition. Next, the film composition was coated on a copper foil (manufactured and sold by guhe electric industry co., ltd.). Then, the copper foil is gradually heated to perform a crosslinking reaction on the film composition at 230 ℃ to obtain a film layer. Next, the refractive index of the film was measured by a reflection type film thickness measuring instrument, and the glass transition temperature of the film was measured by a differential scanning calorimeter, and the results are shown in table 2.
Example 4
The procedure was carried out as described in example 1, except that the ratio of oligomer (I) to triallylisocyanurate was adjusted from 9:1 to 4:6, to obtain a film composition. Next, the film composition was coated on a copper foil (manufactured and sold by guhe electric industry co., ltd.). Then, the copper foil is gradually heated to perform a crosslinking reaction on the film composition at 230 ℃ to obtain a film layer. Next, the refractive index of the film was measured by a reflection type film thickness measuring instrument, and the glass transition temperature of the film was measured by a differential scanning calorimeter, and the results are shown in table 2.
Example 5
The procedure was carried out as described in example 1, except that the ratio of oligomer (I) to triallylisocyanurate was adjusted from 9:1 to 3:7, to obtain a film composition. Next, the film composition was coated on a copper foil (manufactured and sold by guhe electric industry co., ltd.). Then, the copper foil is gradually heated to perform a crosslinking reaction on the film composition at 230 ℃ to obtain a film layer. Next, the refractive index of the film was measured by a reflection type film thickness measuring instrument, and the glass transition temperature of the film was measured by a differential scanning calorimeter, and the results are shown in table 2.
Comparative example 2
The procedure was carried out as described in example 1, except that the ratio of oligomer (I) to triallylisocyanurate was adjusted from 9:1 to 2:8, to give a film composition. Next, the film composition was coated on a copper foil (manufactured and sold by guhe electric industry co., ltd.). Then, the copper foil was gradually heated to perform a crosslinking reaction of the film composition at 230 ℃, and a film could not be obtained. .
Comparative example 3
Oligomer (IV) (50 parts by weight), triallyl isocyanurate (50 parts by weight), and an initiator (1 part by weight,
Figure BDA0002223131520000211
was charged into a reaction flask, and xylene was added to dissolve (30 parts by weight). After stirring uniformly, a film composition is obtained. Next, the film composition was coated on a copper foil (sold by Kogaku electric industries Co., Ltd.). Then, the copper foil is gradually heated to perform a crosslinking reaction on the film composition at 230 ℃, and a film cannot be obtained.
Example 6
Oligomer (VI) (50 parts by weight), triallyl isocyanurate (50 parts by weight), and an initiator (1 part by weight,
Figure BDA0002223131520000212
was charged into a reaction flask, and xylene was added to dissolve (30 parts by weight). After stirring uniformly, a film composition was obtained. Next, the film composition was coated on a copper foil (manufactured and sold by guhe electric industry co., ltd.). Then, the copper foil is gradually heated to perform a crosslinking reaction on the film composition at 230 ℃ to obtain a film layer. Then, the refractive index of the film layer is measured by a reflection type film thickness measuring instrument, and the differential scanning calorimeter is used for measuring the refractive index of the film layerGlass transition temperature, results are shown in Table 2.
Example 7
The procedure was carried out as described in example 6, except that oligomer (VI) was replaced with oligomer (II), to obtain a film composition. Next, the film composition was coated on a copper foil (manufactured and sold by guhe electric industry co., ltd.). Then, the copper foil is gradually heated to perform a crosslinking reaction on the film composition at 230 ℃ to obtain a film layer. Next, the refractive index of the film layer was measured by a reflection type film thickness measuring instrument, and the glass transition temperature of the film layer was measured by a differential scanning calorimeter, and the results are shown in table 2.
Example 8
The procedure was carried out as described in example 6, except that oligomer (VI) was replaced with oligomer (III), to obtain a film composition. Next, the film composition was coated on a copper foil (manufactured and sold by guhe electric industry co., ltd.). Then, the copper foil is gradually heated to perform a crosslinking reaction on the film composition at 230 ℃ to obtain a film layer. Next, the refractive index of the film was measured by a reflection type film thickness measuring instrument, and the glass transition temperature of the film was measured by a differential scanning calorimeter, and the results are shown in table 2.
Example 9
The procedure was carried out as described in example 6, except that oligomer (VI) was replaced with oligomer (VII), to obtain a film composition. Next, the film composition was coated on a copper foil (manufactured and sold by guhe electric industry co., ltd.). Then, the copper foil is gradually heated to perform a crosslinking reaction on the film composition at 230 ℃ to obtain a film layer. Next, the refractive index of the film was measured by a reflection type film thickness measuring instrument, and the glass transition temperature of the film was measured by a differential scanning calorimeter, and the results are shown in table 2.
Comparative example 4
The procedure was carried out as described in example 6, except that oligomer (VI) was replaced with oligomer (V), to obtain a film composition. Next, the film composition was coated on a copper foil (manufactured and sold by guhe electric industry co., ltd.). Then, the copper foil was gradually heated to perform a crosslinking reaction of the film composition at 230 ℃, and a film could not be obtained.
TABLE 2
Figure BDA0002223131520000221
Example 10
Oligomer (II) (90 parts by weight), triallyl cyanurate (TAC) (10 parts by weight), and an initiator (1 part by weight,
Figure BDA0002223131520000231
was charged into a reaction flask, and xylene was added to dissolve (30 parts by weight). After stirring uniformly, a film composition was obtained. Next, the film composition was coated on a copper foil (manufactured and sold by guhe electric industry co., ltd.). Then, the copper foil is gradually heated to perform a crosslinking reaction on the film composition at 230 ℃ to obtain a film layer. Next, the refractive index of the film was measured by a reflection type film thickness measuring instrument, and the glass transition temperature of the film was measured by a differential scanning calorimeter, and the results are shown in table 3.
Example 11
The procedure is as described in example 10, except that triallyl cyanurate (TAC) is replaced with trimethylallyl isocyanurate (TMAIC). Next, the film composition was coated on a copper foil (manufactured and sold by guhe electric industry co., ltd.). Then, the copper foil is gradually heated to perform a crosslinking reaction on the film composition at 230 ℃ to obtain a film layer. Next, the refractive index of the film was measured by a reflection type film thickness measuring instrument, and the glass transition temperature of the film was measured by a differential scanning calorimeter, and the results are shown in table 3.
Example 12
Oligomer (VI) (50 parts by weight), Divinylbenzene (DVB) (50 parts by weight), and initiator (1 part by weight,
Figure BDA0002223131520000232
was charged into a reaction flask, and xylene was added to dissolve (30 parts by weight). After stirring uniformly, a film composition was obtained. Next, the film composition was coated on a copper foil (manufactured and sold by guhe electric industry co., ltd.). Then, the copper foil is gradually heated to perform a crosslinking reaction on the film composition at 230 ℃ to obtain a film layer. Next, the refractive index of the film was measured by a reflection type film thickness measuring instrument, and the glass transition temperature of the film was measured by a differential scanning calorimeter, and the results are shown in table 3.
Example 13
The procedure was followed as described in example 10, except that triallyl cyanurate (TAC) was substituted with N, N '-bismaleimide-4, 4' -diphenylmethane (N, N '-bismaleimide-4, 4' -diphenylmethane). Next, the film composition was coated on a copper foil (manufactured and sold by guhe electric industry co., ltd.). Then, the copper foil is gradually heated to perform a crosslinking reaction on the film composition at 230 ℃ to obtain a film layer. Next, the refractive index of the film was measured by a reflection type film thickness measuring instrument, and the glass transition temperature of the film was measured by a differential scanning calorimeter, and the results are shown in table 3.
Example 14
The procedure is as described in example 10, except that triallyl cyanurate (TAC) is replaced with pentaerythritol tetraacrylate (PETTA). Next, the film composition was coated on a copper foil (manufactured and sold by guhe electric industry co., ltd.). Then, the copper foil is gradually heated to perform a crosslinking reaction on the film composition at 230 ℃ to obtain a film layer. Next, the refractive index of the film was measured by a reflection type film thickness measuring instrument, and the glass transition temperature of the film was measured by a differential scanning calorimeter, and the results are shown in table 3.
Example 15
Oligomer (III) (80 parts by weight), tris (2-hydroxyethyl) isocyanurate triacrylate (SR368) (20 parts by weight), and initiator (1 part by weight,
Figure BDA0002223131520000241
was charged into a reaction flask, and xylene was added to dissolve (30 parts by weight). After stirring uniformly, a film composition was obtained. Next, the film composition was coated on a copper foil (manufactured and sold by guhe electric industry co., ltd.). Then, the copper foil is gradually heated to perform a crosslinking reaction on the film composition at 230 ℃ to obtain a film layer. Next, the refractive index of the film was measured by a reflection type film thickness measuring instrument, and the glass transition temperature of the film was measured by a differential scanning calorimeter, and the results are shown in table 3.
Example 16
The procedure was as described in example 10, except that triallyl cyanurate (TAC) was substituted with bis (vinylphenyl) ethane (BVPE). Next, the film composition was coated on a copper foil (manufactured and sold by guhe electric industry co., ltd.). Then, the copper foil is gradually heated to perform a crosslinking reaction on the film composition at 230 ℃ to obtain a film layer. Next, the refractive index of the film was measured by a reflection type film thickness measuring instrument, and the glass transition temperature of the film was measured by a differential scanning calorimeter, and the results are shown in table 3.
Example 17
The procedure is as described in example 15, except that tris (2-hydroxyethyl) isocyanurate triacrylate (SR368) is replaced with tricyclodecane dimethanol diacrylate (SR 833S). Next, the film composition was coated on a copper foil (manufactured and sold by guhe electric industry co., ltd.). Then, the copper foil is gradually heated to perform a crosslinking reaction on the film composition at 230 ℃ to obtain a film layer. Next, the refractive index of the film was measured by a reflection type film thickness measuring instrument, and the glass transition temperature of the film was measured by a differential scanning calorimeter, and the results are shown in table 3.
Example 18
Oligomer (II) (70 parts by weight), 1,2,4-Trivinylcyclohexane (TVCH) (30 parts by weight), and an initiator (1 part by weight,
Figure BDA0002223131520000242
was charged into a reaction flask, and xylene was added to dissolve (30 parts by weight). After stirring uniformly, a film composition was obtained. Next, the film composition was coated on a copper foil (manufactured and sold by guhe electric industry co., ltd.). Then, the copper foil is gradually heated to perform a crosslinking reaction on the film composition at 230 ℃ to obtain a film layer. Next, the refractive index of the film was measured by a reflection type film thickness measuring instrument, and the glass transition temperature of the film was measured by a differential scanning calorimeter, and the results are shown in table 3.
Example 19
The procedure was followed as described in example 10, except that triallyl cyanurate (TAC) was substituted with dipentaerythritol hexaacrylate (DPHA). Next, the film composition was coated on a copper foil (manufactured and sold by guhe electric industry co., ltd.). Then, the copper foil is gradually heated to perform a crosslinking reaction on the film composition at 230 ℃ to obtain a film layer. Next, the refractive index of the film was measured by a reflection type film thickness measuring instrument, and the glass transition temperature of the film was measured by a differential scanning calorimeter, and the results are shown in table 3.
TABLE 3
Figure BDA0002223131520000251
Figure BDA0002223131520000261
Example 20
Oligomer (VIII) (70 parts by weight), Divinylbenzene (DVB) (30 parts by weight), and initiator (1 part by weight,
Figure BDA0002223131520000262
was charged into a reaction flask, and xylene was added to dissolve (30 parts by weight). After stirring uniformly, a film composition was obtained. Next, the film composition was coated on a copper foil (manufactured and sold by guhe electric industry co., ltd.). Followed byAnd gradually heating the copper foil to perform a crosslinking reaction on the film composition at 230 ℃ to obtain a film layer. Next, the refractive index of the film was measured by a reflection type film thickness measuring instrument, and the glass transition temperature of the film was measured by a differential scanning calorimeter, and the results are shown in table 4.
Example 21
Oligomer (X) (50 parts by weight), triallyl isocyanurate (50 parts by weight), and an initiator (1 part by weight,
Figure BDA0002223131520000263
was charged into a reaction flask, and xylene was added to dissolve (30 parts by weight). After stirring uniformly, a film composition was obtained. Next, the film composition was coated on a copper foil (manufactured and sold by guhe electric industry co., ltd.). Then, the copper foil is gradually heated to perform a crosslinking reaction on the film composition at 230 ℃ to obtain a film layer. Next, the refractive index of the film was measured by a reflection type film thickness measuring instrument, and the glass transition temperature of the film was measured by a differential scanning calorimeter, and the results are shown in table 4.
Example 22
The procedure is as described in example 21, except that oligomer (X) is replaced with oligomer (XI). Next, the film composition was coated on a copper foil (manufactured and sold by guhe electric industry co., ltd.). Then, the copper foil is gradually heated to perform a crosslinking reaction on the film composition at 230 ℃ to obtain a film layer. Next, the refractive index of the film was measured by a reflection type film thickness measuring instrument, and the glass transition temperature of the film was measured by a differential scanning calorimeter, and the results are shown in table 4.
Example 23
Oligomer (XII) (50 parts by weight), Divinylbenzene (DVB) (50 parts by weight), and initiator (1 part by weight,
Figure BDA0002223131520000264
was charged into a reaction flask, and xylene was added to dissolve (30 parts by weight). After being stirred evenly, a film is obtainedA composition is provided. Next, the film composition was coated on a copper foil (manufactured and sold by guhe electric industry co., ltd.). Then, the copper foil is gradually heated to perform a crosslinking reaction on the film composition at 230 ℃ to obtain a film layer. Next, the refractive index of the film was measured by a reflection type film thickness measuring instrument, and the glass transition temperature of the film was measured by a differential scanning calorimeter, and the results are shown in table 4.
Example 24
Oligomer (XIII) (60 parts by weight), triallyl isocyanurate (40 parts by weight), and initiator (1 part by weight,
Figure BDA0002223131520000272
was charged into a reaction flask, and xylene was added to dissolve (30 parts by weight). After stirring uniformly, a film composition was obtained. Next, the film composition was coated on a copper foil (manufactured and sold by guhe electric industry co., ltd.). Then, the copper foil is gradually heated to perform a crosslinking reaction on the film composition at 230 ℃ to obtain a film layer. Next, the refractive index of the film was measured by a reflection type film thickness measuring instrument, and the glass transition temperature of the film was measured by a differential scanning calorimeter, and the results are shown in table 4.
Example 25
Oligomer (XIV) (40 parts by weight), triallyl isocyanurate (60 parts by weight), and an initiator (1 part by weight,
Figure BDA0002223131520000273
was charged into a reaction flask, and xylene was added to dissolve (30 parts by weight). After stirring uniformly, a film composition was obtained. Next, the film composition was coated on a copper foil (manufactured and sold by guhe electric industry co., ltd.). Then, the copper foil is gradually heated to perform a crosslinking reaction on the film composition at 230 ℃ to obtain a film layer. Next, the refractive index of the film was measured by a reflection type film thickness measuring instrument, and the glass transition temperature of the film was measured by a differential scanning calorimeter, and the results are shown in table 4.
Example 26
The procedure is as described in example 2, except that oligomer (I) is substituted with oligomer (XV). Next, the film composition was coated on a copper foil (manufactured and sold by guhe electric industry co., ltd.). Then, the copper foil is gradually heated to perform a crosslinking reaction on the film composition at 230 ℃ to obtain a film layer. Next, the refractive index of the film was measured by a reflection type film thickness measuring instrument, and the glass transition temperature of the film was measured by a differential scanning calorimeter, and the results are shown in table 4.
TABLE 4
Figure BDA0002223131520000271
Figure BDA0002223131520000281
Although the present disclosure has been described with reference to several embodiments, it should be understood that various changes and modifications can be made by one skilled in the art without departing from the spirit and scope of the disclosure, and therefore the scope of the disclosure should be determined by that of the appended claims.

Claims (14)

1. A film composition comprising:
a crosslinking agent; and
an oligomer, wherein the weight ratio of the oligomer to the crosslinker is 9:1 to 3:7, wherein the crosslinker is a compound or bismaleimide having at least two crosslinkable functional groups, wherein the crosslinkable functional groups are alkenyl groups, methacrylate groups, acrylate groups, acryloyl groups, epoxy groups, carboxyl groups, or a combination thereof, wherein the oligomer has a number average molecular weight (Mn) of 1,000 to 8,000, wherein the oligomer has a structure represented by formula (I)
Figure FDA0002223131510000011
Wherein R is1And R2Independently of each other is hydrogen, C1-20Alkyl radical, C2-20Alkenyl radical, C6-12Aryl radical, C6-12Alkylaryl group, C5-12Cycloalkyl radical, C6-20Cycloalkylalkyl, alkoxycarbonyl, or alkylcarbonyloxy; r1And R2Not hydrogen at the same time; a is 0 or 1; n is not less than 0; m ≧ 1, wherein when n is not 0, n: m is 3:1 to 1: 4; and the repeating unit
Figure FDA0002223131510000012
And the repeating unit
Figure FDA0002223131510000013
Repeating in a random manner or in a block manner.
2. The film composition of claim 1, wherein R1And R2Independently of one another is hydrogen, or
Figure FDA0002223131510000014
Wherein b is 0, or an integer from 1 to 19; and, R1And R2Not hydrogen at the same time.
3. The film composition of claim 1, wherein R1And R2Independently of one another is hydrogen, or
Figure FDA0002223131510000021
Wherein c is 0, or an integer from 1 to 6; and, R1And R2Not hydrogen at the same time.
4. The film composition of claim 1, wherein R1And R2Independently of one another is hydrogen, or
Figure FDA0002223131510000022
And wherein d is 0, or an integer from 1 to 6; and, R1And R2Not hydrogen at the same time.
5. The film composition of claim 1, wherein R1And R2Independently of one another is hydrogen, or
Figure FDA0002223131510000023
Wherein e is 0, or an integer from 1 to 6; and, R1And R2Not hydrogen at the same time.
6. The film composition of claim 1, wherein R1And R2Independently of one another is hydrogen, or
Figure FDA0002223131510000024
And wherein f is 0, or an integer from 1 to 6; r3Is C1-6An alkyl group; and, R1And R2Not hydrogen at the same time.
7. The film composition of claim 1, wherein R1And R2Independently of one another is hydrogen, or
Figure FDA0002223131510000025
And wherein g is 0, or an integer from 1 to 6; r4Is C1-6An alkyl group; and, R1And R2Not hydrogen at the same time.
8. The film composition of claim 1, wherein R1And R2Independently of one another is hydrogen, or
Figure FDA0002223131510000026
Wherein h is an integer from 1 to 6; and, R1And R2Not hydrogen at the same time.
9. The film composition of claim 1, wherein R1And R2Independently of one another is hydrogen, or
Figure FDA0002223131510000031
Wherein i is 0, 1,2, 3,4.5, or 6; and, R1And R2Not hydrogen at the same time.
10. The film composition of claim 1, wherein R1And R2Independently of one another is hydrogen, or
Figure FDA0002223131510000032
Wherein j is 0, 1,2, 3, 4,5, or 6; and, R1And R2Not hydrogen at the same time.
11. The film composition of claim 1, further comprising a solvent, wherein the ratio of the weight of the solvent to the total weight of the oligomer and the crosslinker is from 0.01 to 60.
12. The film composition of claim 1, wherein the crosslinker is a bismaleimide having the structure of formula (II) or formula (III)
Figure FDA0002223131510000033
Wherein R is5is-CR2-、-NR-、-C(O)CH2-、-CH2OCH2-、-C(O)-、-O-、-O-O-、-S-、-S-S-、-S(O)-、-CH2S(O)CH2-、-(O)S(O)-、-C6R4-、-CH2(C6R4)CH2-、-CH2(C6R4) (O) -, substituted or unsubstituted biphenylene (diphenylene), R6is-CR2-, -C (O) -, -O-, -S-, - (O) S (O) -, or-S (O) -; and R is independently hydrogen or C1-4An alkyl group.
13. The film composition of claim 1, wherein the cross-linking agent is N, N '-bismaleimide-4, 4' -diphenylmethane (N, N '-bismaleimide-4, 4' -diphenylmethanide), 1,1 '- (methylenebis-4, 1-phenylene) bismaleimide (1, 1' - (methylene di-4,1-phenylene) bisimide), N, N '- (1, 1' -biphenyl-4,4 '-diyl) bismaleimide (N, N' - (1,1 '-bipheny 1-4, 4' -diyl) bismaleimide), N, N '- (4-methyl-1,3-phenylene) bismaleimide (N, N' - (4-methyl-1,3-phenylene) bisimide), 1,1 '- (3, 3' -dimethyl-1, 1 '-biphenyl-4, 4' -diyl) bismaleimide (1,1 '- (3, 3' -dimethyl-1, 1 '-biphenyl-4, 4' -diyl) bismaleimide), N, N '-ethylenebismaleimide (N, N' -ethylenebismaleimide), N, N '- (1,2-phenylene) bismaleimide (N, N' - (1,2-phenylene) bismaleimide), N, N '- (1,3-phenylene) bismaleimide (N, N' - (1,3-phenylene) bismaleimide), N, N '-bismaleimide sulfide (N, N' -thiobismaleimide), N, N '-bismaleimide disulfide (N, N' -bismaleimide), N, n '-bismaleimide ketone (N, N' -ketonedimaleimide), N '-methylenebismaleimide (N, N' -methyl-bis-maleimide), bismaleimide methyl-ether (bis-maleinimidopropyl-ether), 1, 2-bismaleimide-1, 2-ethanediol (1,2-bis- (maleinido) -1, 2-ethanediol), N '-4, 4' -diphenyl ether-bismaleimide (N, N '-4, 4' -diphenyletherbismaleimide), or 4,4 '-bismaleimide-diphenyl sulfone (4, 4' -bis- (maleinido) -phenylsulfone).
14. A film which is a cured product of the film composition according to any one of claims 1 to 13.
CN201910941870.1A 2018-10-05 2019-09-30 Film composition and film formed therefrom Pending CN111004530A (en)

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Citations (6)

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US7253245B2 (en) * 2004-06-02 2007-08-07 Acushnet Company Compositions for golf equipment
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CN103013206A (en) * 2011-09-27 2013-04-03 住友化学株式会社 Composition for optical film and optical film thereof
CN105555814A (en) * 2013-08-22 2016-05-04 汉高知识产权控股有限责任公司 High molecular weight polymers having high olefin content
CN106893092A (en) * 2015-12-18 2017-06-27 台光电子材料(昆山)有限公司 The polyphenylene oxide of phenol containing fluorenes
CN107417891A (en) * 2016-12-29 2017-12-01 财团法人工业技术研究院 Oligomer, the composition and composite for including it

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US7253245B2 (en) * 2004-06-02 2007-08-07 Acushnet Company Compositions for golf equipment
CN102115569A (en) * 2009-12-31 2011-07-06 财团法人工业技术研究院 Dielectric material composition and circuit substrate
CN103013206A (en) * 2011-09-27 2013-04-03 住友化学株式会社 Composition for optical film and optical film thereof
CN105555814A (en) * 2013-08-22 2016-05-04 汉高知识产权控股有限责任公司 High molecular weight polymers having high olefin content
CN106893092A (en) * 2015-12-18 2017-06-27 台光电子材料(昆山)有限公司 The polyphenylene oxide of phenol containing fluorenes
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