TW202003678A - Curable compositions - Google Patents

Abstract

The present disclosure relates to monomers, oligomers and polymers useful as additives for adhesive and/or sealant compositions, and particularly to one drop fill ("ODF") sealant compositions for liquid crystal display applications. The present disclosure permits assembly of liquid crystal display ("LCD") panels with little to no migration of the sealant composition into the liquid crystal, or vice versa, during LCD assembly and/or curing of the sealant composition.

Description

Curable composition

The present invention relates to monomers, oligomers and polymers suitable for use as additives in adhesive and/or sealant compositions, and specifically relates to drop-in injection ("ODF") sealing for liquid crystal display applications剂组合物。 Agent composition. The present invention makes it possible to assemble a liquid crystal display ("LCD") panel in a state where the sealant composition hardly migrates into liquid crystal or vice versa during LCD assembly and/or curing of the sealant composition.

The ODF process is becoming the mainstream process for the assembly of LCD panels in display applications. It replaces the conventional vacuum injection technology to meet the needs of faster manufacturing processes. In the ODF process, the sealant is distributed on the substrate equipped with the first electrode to form the frame of the display device. Then, the liquid crystal drops inside the formed frame. In the next step of assembly, the substrate equipped with the other electrode is bonded to the substrate equipped with the first electrode under vacuum. Then, the sealant is cured by a combination of UV and thermal processes or only by thermal processes.

There are several problems with the ODF process. The sealant material in the uncured state comes into contact with the liquid crystal during the assembly process. The migration of the sealant material into the liquid crystal or the liquid crystal into the uncured sealant material may reduce the electro-optical characteristics of the liquid crystal. Therefore, the design of sealant materials showing good liquid crystal tolerance (ie, less contamination) is of primary importance. Disadvantageously, it is still challenging.

To date, although it has been desired to provide curable resin systems with less sealant migration into adjacent liquid crystals, and vice versa, no suitable solution has been provided.

The present invention relates to curable compositions including additives that provide adhesion and/or sealing performance. In one aspect, the curable composition of the present invention can be applied as an ODF sealant composition with improved performance.

According to the present invention, in one embodiment, the curable composition includes a curable resin, a polyamide additive, and a curing agent.

According to the present invention, in another embodiment, the curable composition includes a curable resin, a star polymer additive, and a curing agent. The star polymer additive includes a core formed by a network structure of crosslinked polymers and a plurality of linear polymer chains (arms) extending from the core.

According to the present invention, in yet another embodiment, the curable composition includes a curable resin, a comb polymer additive, and a curing agent. The comb polymer additive is composed of a main chain having two or more three-way branch points and a linear side chain extending from each branch point.

According to the present invention, in yet another embodiment, the curable composition includes a curable resin, a repeatedly branched dendrimer additive, and a curing agent.

According to the present invention, in yet another embodiment, the curable composition includes: (a) a curable epoxy-functionalized resin based on bisphenol A, bisphenol F, bisphenol S, phenol-novolac, bicyclic Pentadiene, naphthalene, or a mixture of any two or more thereof; (b) additives, the volume of which expands with increasing temperature and is between 25°C and 65°C relative to the curable composition without additives Provides 1 to 100 times improved viscosity drop resistance for the curable composition in the temperature range; and (c) curing agent.

According to the present invention, there is provided a method for synthesizing a star polymer, which comprises: providing (meth)acrylate (such as tertiary butyl acrylate); injecting an initiator to produce a mixture; and combining a ligand (such as ginseng [2 -(Dimethylamino)ethyl]amine) is injected into the mixture to form a star polymer core. In an embodiment, the method of the present invention achieves greater than 85% conversion of (meth)acrylate (from (meth)acrylate to core network structure of cross-linked polymer). Next, (meth)acrylate (such as n-butyl acrylate) and additional ligands are added to the core to form an isoarm, and the resulting star polymer is isolated. In an embodiment, the method of the present invention also achieves greater than 85% conversion of (meth)acrylate (from (meth)acrylate to a plurality of linear polymer chains).

According to the present invention, a method of imparting improved tack resistance to a curable composition includes: providing a curable epoxy-functionalized resin based on bisphenol A, bisphenol F, and bisphenol Phenol S, phenol-novolac, dicyclopentadiene, naphthalene or a mixture of any two or more of them; provide a curing agent; and add an expandable viscosity modifier additive, in which the volume of the expandable viscosity modifier additive increases As temperature increases, it expands. Compared to curable compositions without additives, the swellable viscosity modifier additive provides at least 2 times improved resistance to sudden viscosity drop from the first lower temperature condition to the second higher temperature condition. Compared to curable compositions without additives, swellable viscosity modifier additives provide a greater viscosity index, sometimes to a level close to 1.0, and in some cases to a level greater than 1.0 (meaning the viscosity is at a higher temperature Add below). It can be found that the temperature range within these two temperature conditions is from about room temperature (25°C) to cured Tonset, which will depend on the nature and properties of the reactive ingredients in the composition. In a particular application, Tonset can be about 65°C. The viscosity index ("VI") is the ratio of the viscosity at a higher temperature divided by the viscosity at a lower temperature. Generally, the curable composition VI of the present invention is less than 1.0, although sometimes it exceeds 1.0.

Other features and advantages of the present invention should become apparent in view of the following description of non-limiting embodiments.

Viscosity is a measure of the resistance to gradual deformation caused by shear stress or tensile stress. For liquid, it corresponds to the informal concept of "thickness". For example, at ambient temperature, honey has a much higher viscosity than water.

The curing behavior of different thermosetting resin formulations conforms to a similar profile, because when heat is applied, the resin viscosity initially decreases, passes through the maximum flow area (where the resin viscosity continues to decrease), and then forms a polymer network structure as the chemical reaction increases The average length and the degree of crosslinking between the component monomers and/or oligomers begin to increase. The viscosity continues to increase until a continuous three-dimensional network structure of monomer and/or oligomer chains is produced. This conversion is called gelation.

In one aspect of the invention, it is disclosed that maintaining a high viscosity of the curable composition during LCD assembly and/or curing of the resin and in practice reducing the penetration of the curable composition into the liquid crystal (or vice versa) additive. These additives exhibit a sudden drop in viscosity, (1) reducing the initial resin viscosity drop and (2) reducing the viscosity drop during the maximum flow area. These characteristics are particularly desirable in ODF sealant compositions.

In addition, the volume of additives increases with increasing temperature. For example, the additives of the present invention may spiral at low temperatures and then expand at increased temperatures.

In an embodiment, the additive may be used in an amount of about 0.1% to about 20% by weight of the curable composition. In an embodiment, the additive may be used in an amount of about 0.1% to about 10% by weight of the curable composition. In an embodiment, the additive may be used in an amount of about 0.1% to about 5% by weight of the curable composition.

These additives can also be called "gelling agents".

As mentioned above, according to the present invention, the curable composition includes a curable resin, a polyamide additive, and a curing agent.

其中： R為約1至約20個碳單元之烷基鍵或芳基鍵；及 n為約1至約50。In one aspect of the invention, the polyamide additive has the following structure:

Where: R is an alkyl bond or aryl bond of about 1 to about 20 carbon units; and n is about 1 to about 50.

In some embodiments, the polyamide additive is primarily aliphatic, providing improved dissolution characteristics. In an embodiment, R is an aliphatic chain containing one or more oxygen atoms, sulfur atoms, and/or nitrogen atoms.

In some embodiments, the polyamide additive is aromatic, where R is an aromatic ring, such as furan, benzofuran, isobenzofuran, pyrrole, indole, isoindole, thiophene, benzothiophene, benzo[ c] Thiophene, imidazole, benzimidazole, purine, pyrazole, indazole, oxazole, benzoxazole, isoxazole, benzisoxazole, thiazole, benzthiazole, benzene, naphthalene, anthracene, pyridine, Quinolinone, isoquinoline, pyrazine, quinoxaline, acridine, pyrimidine, quinazoline, pyridazine, cinnoline, phthalazine, 1,2,3-triazine, 1,2,4-triazine , 1,3,5-triazine (all triazine) and the like.

Examples of polyamide additives include: Crayvallac® SF, Crayvallac® 60P, Crayvallac® 60X, E00075 and the like manufactured by Arkema (King of Prussia, PA), and BYK-R manufactured by BYK Chemie (Wallingford, CT) 605, BYK-R 606, BYK-R 607, BYK 425, BYK 428 and the like.

Crayvallac® SF is reported by the manufacturer as a amide-modified hydrogenated castor oil rheology modifier. It can be used as an "off-white" powder with enhanced resistance to temperature and solvent strength. Compared to other rheology modifiers based on hydrogenated castor oil, Crayvallac® SF is reported by the manufacturer as being more resistant to stronger solvents and higher processing temperatures due to the presence of its amide. Using the Malvern Mastersizer S laser particle size analyzer, manufacturers report particle sizes between about 4 µm and about 20 µm. In addition, using differential scanning calorimetry (DSC), the melting point of Crayvallac® SF is between about 130°C and about 140°C and its density is about 1.02 g/cm ³ at 25°C.

Crayvallac® 60P is reported by the manufacturer as a solid powder composed of fine particles of oxidized polyethylene. It is mainly used in industrial and maintenance coatings, where its main function is to provide a pigment suspension without ignoring any increase in viscosity. Typical applications of Crayvallac® 60P are epoxy primers, vinyl primers, antifouling pigments, road marking pigments and chlorinated rubber coatings. Using the Malvern Mastersizer S laser particle size analyzer, the manufacturer reported that the particle size of Crayvallac® 60P is less than about 7 µm, and its density is about 0.93 g/cm ³ at 25°C.

Crayvallac® 60X is reported by the manufacturer as a waxy solid slurry consisting of extremely fine droplets of oxidized polyethylene dispersed in xylene, and has a density of about 0.87 g/cm ³ at 25°C.

E00075 was reported by the manufacturer as a polyamide-based gelling agent dispersed in acrylate resin. More specifically, the manufacturer reports that E00075 is a mixture of Crayvallac® SF (approximately 20%) and acrylate resin (approximately 80% 4-tributylcyclohexyl acrylate).

BYK-R 605 is reported by the manufacturer as a solution of polyhydroxycarboxylic acid amides and is commonly used in plastic applications such as vinyl ester and epoxy resins, unsaturated polyester resins and gel coatings to reinforce pyrolytic dioxide Rheological effect of silicon. For example, BYK-R 605 is reported to be used in unsaturated polyester resins, epoxy resins, and polyurethane systems to reinforce the three-dimensional network structure of silica or phyllosilicate through additional bridging, thus Enhance shakeability. Its density is about 0.93 g/cm ³ at 20°C.

BYK-R 606 is reported by the manufacturer as a liquid polyhydroxycarboxylate. The manufacturer reports that it strengthens the hydrogen bonding of silicon oxide and phyllosilicate, resulting in increased shakeability. Its density is about 1.01 g/cm ³ at 20°C.

BYK-R 607 is reported by the manufacturer as a solution of amine-functional oligomeric amide. The manufacturer reports that it reinforces the network structure produced by the thixotropic glue, thereby ensuring that the network structure does not break as usual when the amine hardener is added. BYK-R 607 reportedly enables the use of hydrophilic fumed silica or clay additives only in two-component epoxy systems. Its density is about 0.98 g/cm ³ at 20°C.

BYK 425 was reported by the manufacturer as a solution of urea-modified polyurethane. Its density is about 8.68 at 68°F in lbs/US gallons. BYK 425 is usually solvated with polypropylene glycol.

BYK 428 is reported by the manufacturer as a solution of polyurethane with a highly branched structure. Its density is approximately 8.76 at 68°F in lbs/US gallons. BYK 428 is usually solvated with water and/or ethoxylate.

Polyamide is generally a macromolecule having repeating units connected by an amide bond. It can occur naturally or be synthesized. Examples of naturally occurring polyamides are proteins, such as cotton wool and silk. Synthetic polyamide can be made by step-wise growth polymerization or solid-phase synthesis to obtain materials such as nylon, aromatic polyamide and poly(aspartic acid) sodium. These latter polyamides are commonly used in fabrics, automotive applications, carpets and sportswear due to their high durability and strength.

Polyamide additives used in the present invention can be added to, for example, curable resins, such as based on bisphenol A, bisphenol F, bisphenol S, phenol novolac, dicyclopentadiene, naphthalene, or any two or Epoxy-functionalized resins of more mixtures.

In another aspect, the star polymer includes a core formed by a network structure of cross-linked polymers and a plurality of linear polymer chains (arms) extending from the core.

As the temperature increases, the star polymer can increase its hydrodynamic radius and thus its volume. Higher molecular weight star polymers with longer (and higher molecular weight) arms can provide an increase in volume change each time the temperature is increased. However, star polymers with excessively high molecular weight (ie, about 600 kDA) may be difficult to dissolve to form a solution. Therefore, the star polymer additive used in the present invention achieves a balance between large volume change and solubility.

In an embodiment, the star polymer has a core: arm ratio of between about 1:20 in terms of molecular weight. In an embodiment, the core:arm ratio is between about 5:15. Therefore, in some embodiments, the molecular weight of the core may be approximately 10 to 20 times the molecular weight of the plurality of linear polymer chains extending from the core.

In an embodiment, the plurality of polymer chains are acrylate polymer chains, which provide a consistent interaction between the star polymer additive and the functionalized curable resin.

In an embodiment, the acrylate polymer chain is connected to the core by reaction with α-bromo-ester. In an embodiment, the core is formed by copolymerizing a block copolymer connected by P-1,6-hexanediol diacrylate-P', and P and P'are each copolymers that may be the same or different.

Compared to linear analogues and/or monomer compositions of the same molecular weight, some of the more significant features exhibited by the star polymers of the present invention are their unique viscosity modifying properties. In addition, star polymers exhibit lower melting temperatures and lower crystallization temperatures than comparable linear analogs.

In general, star polymers have a smaller hydrodynamic radius than their linear analogs of the same molecular weight. In the present invention, the hydrodynamic radius is the equivalent hard sphere radius of the observed molecule.

The orientation of terminal polar groups (eg, hydroxyl or carboxylic acid) can affect the sudden drop in viscosity. The polar group at the end of the linear polymer chain arm (i.e., the outer shell of the star polymer) often helps to improve the viscosity drop resistance, while at the inner part of the star polymer and connected to the core Polar groups unconventionally exhibit improved resistance to sudden drop in viscosity.

In some embodiments, the end of at least one linear polymer chain further away from the core can be hydrogen bonded via a hydroxyl group.

In some embodiments, the end of at least one linear polymer chain closest to the core is hydrogen bonded to the core.

In one aspect of the present invention, a star polymer additive having a core formed by a network structure of a cross-linked polymer and a plurality of linear polymer chains extending from the core may be added to, for example, a curable resin, Such as epoxy functional resin based on bisphenol A, bisphenol F, bisphenol S, phenol novolak, dicyclopentadiene, naphthalene or a mixture of any two or more thereof.

In yet another aspect, the comb polymer additive is composed of a main chain having two or more three-way branch points and a linear side chain extending from each branch point.

The comb polymer additive can be selected from a large number of materials, and commercially available examples thereof can be derived from Evonik Industries (Essen, Germany), Arkema (King of Prussia, PA), and Chemtura (Middlebury, CT). The following comb polymers are available from Evonik: VISCOPLEX® 3-160, VISCOPLEX® 3-162, VISCOPLEX® 3-200, VISCOPLEX® 3-201, VISCOPLEX® 3-211 and VISCOPLEX® 3-220, and help Adjust the viscosity index of the gasoline used in the engine. Cray Valley also has a polychloroprene polymer that can be used as a comb polymer.

An example of the comb polymer structure of the present invention is described below.

In an embodiment, at least two linear side chains extending from different branch points are the same.

In the embodiment, all straight chain side chains extending from the branch point are the same.

In an embodiment, at least two straight chain side chains extending from the branch point are different.

In the embodiment, all the linear side chains extending from the branch point are different.

Different linear side chains will cause different solubility characteristics and different volume expansion characteristics.

In one aspect of the present invention, the curable composition of the present invention includes: a comb-shaped polymer additive including linear side chains having two or more three-directional branch points and extending from each branch point, The comb polymer additive is added to a curable resin functionalized with a group selected from the group consisting of maleimide, epoxy, (meth)acrylate, vinyl ether, vinyl acetate, Nadi imide, itaconic imide or any two or more of them; and curing agent.

In another aspect, the dendrimer additive is repeatedly branched. Dendrimers are usually symmetrical around the core and usually adopt a spherical three-dimensional morphology. An example of a dendrimer is described below.

In an embodiment, the dendrimer additive of the present invention has a molecular weight between about 10 and about 250 kDa.

Therefore, combinations of various additives described herein can be used in the curable composition of the present invention. That is, two or more additives of polyamide, star polymer, comb polymer, dendrimer may be used.

One aspect of the present invention includes a curable composition suitable as an ODF sealant, which includes a glycidyl ether compound. Examples of compounds available in the market include: bisphenol A type epoxy resins, such as Epikote 828EL and Epikote 1004 (all manufactured by Japan Epoxy Resin Co., Ltd.); bisphenol F type epoxy resins, such as Epikote 806 and Epikote 4004 (all manufactured by Japan Epoxy Resin Co., Ltd.); bisphenol S type epoxy resins, such as Epiclon EXA1514 (manufactured by Dainippon Ink and Chemicals Inc.) and SE 650 (manufactured by Shin A T&C); 2 , 2'-diallyl bisphenol A type epoxy resin, such as RE-81 ONM (manufactured by Nippon Kayaku Co., Ltd.); hydrogenated bisphenol type epoxy resin, such as Epiclon EXA7015 (manufactured by Dainippon Ink and Chemicals Inc.); bisphenol A type epoxy resin added with propylene oxide, such as EP-4000S (manufactured by ADEKA Corporation); resorcinol type epoxy resin, such as EX-201 (manufactured by Nagase ChemteX Corporation ); biphenyl type epoxy resin, such as Epikote YX-4000H (manufactured by Japan Epoxy Resin Co., Ltd.); sulfide type epoxy resin, such as YSLV 50TE (manufactured by Tohto Kasei Co., Ltd.); Ether type epoxy resin, such as YSLV 80DE (manufactured by Tohto Kasei Co., Ltd.); dicyclopentadiene type epoxy resin, such as EP-4088S and EP4088L (manufactured by ADEKA Corporation); naphthalene type epoxy resin, Such as SE-80, SE-90 (manufactured by Shin A T&C); epoxypropylamine type epoxy resin, such as Epikote 630 (manufactured by Japan Epoxy Resin Co., Ltd.), Epiclon 430 (manufactured by Dainippon Ink and Chemicals) Inc.) and TETRAD-X (manufactured by Mitsubishi Gas Chemical Company Inc.); alkyl polyol type epoxy resins such as ZX-1542 (manufactured by Tohto Kasei Co., Ltd.), Epiclon 726 (manufactured by Dainippon Ink and Chemicals Inc.), Epolig ht 8OMFA (manufactured by Kyoeisha Chemical Co., Ltd.) and Denacol EX-611 (manufactured by Nagase ChemteX Corporation); rubber modified type epoxy resins such as YR-450, YR-207 (all by Tohto Kasei Co. , Ltd.) and Epolead PB (manufactured by Daicel Chemical Industries, Ltd.); glycidyl ester compounds such as Denacol EX-147 (manufactured by Nagase ChemteX Corporation); bisphenol A type episulfide resins such as Epikote YL- 7000 (manufactured by Japan Epoxy Resin Co., Ltd.); and others, such as YDC-1312, YSLV-BOXY, YSLV-90CR (all manufactured by Tohto Kasei Co., Ltd.), XAC4151 (manufactured by Asahi Kasei Corporation) Manufactured), Epikote 1031, Epikote 1032 (all manufactured by Japan Epoxy Resin Co., Ltd.), EXA-7120 (manufactured by Dainippon Ink and Chemicals Inc.), TEPIC (manufactured by Nissan Chemical Industries, Ltd.). Examples of commercially available phenol novolak type epoxy compounds include Epiclon N-740, N-770, N-775 (all manufactured by Dainippon Ink and Chemicals Inc.), Epikote 152, Epikote 154 (all manufactured by Japan Epoxy Resin Co., Ltd.) and the like. Examples of commercially available cresol novolac type epoxy compounds include Epiclon N-660, N-665, N-670, N-673, N-680, N-695, N-665-EXP and N-672-EXP ( All are manufactured by Dainippon Ink and Chemicals Inc.); examples of commercially available biphenol novolac type epoxy compounds are NC-3000P (manufactured by Nippon Kayaku Co., Ltd.); commercially available triphenol novolac type epoxy Examples of compounds include EP1032S50 and EP1032H60 (all manufactured by Japan Epoxy Resin Co., Ltd.); examples of commercially available dicyclopentadiene novolac type epoxy compounds include XD-1000-L (by Nippon Kayaku Co., Ltd.) and HP-7200 (manufactured by Dainippon Ink and Chemicals Inc.); examples of commercially available bisphenol A type epoxy compounds include Epikote 828, Epikote 834, Epikote 1001, and Epikote 1004 (all made by Japan Epoxy Resin Co. ., Ltd.); Epiclon 850, Epiclon 860, and Epiclon 4055 (all manufactured by Dainippon Ink and Chemicals Inc.); examples of commercially available bisphenol F type epoxy compounds include Epikote 807 (manufactured by Japan Epoxy Resin Co., Ltd.) and Epiclon 830 (manufactured by Dainippon Ink and Chemicals Inc.); examples of commercially available 2,2'-diallylbisphenol A type epoxy compounds are RE-81ONM (manufactured by Nippon Kayaku Co., Ltd. Manufacturing); Examples of commercially available hydrogenated bisphenol type epoxy compounds are ST-5080 (manufactured by Tohto Kasei Co., Ltd.); Examples of commercially available polypropylene oxide bisphenol A type epoxy compounds include EP-4000 And EP-4005 (all manufactured by ADEKA Corporation); and the like. HP4032 and Epiclon EXA-4700 (all manufactured by Dainippon Ink and Chemicals Inc.); phenol novolac type epoxy resin, such as Epiclon N-770 (manufactured by Dainippon Ink and Chemicals Inc.); o-cresol novolac type ring Oxygen resins, such as Epiclon N-670-EXP-S (manufactured by Dainippon Ink and Chemicals Inc.); dicyclopentadiene novolac type epoxy resins, such as Epiclon HP7200 (manufactured by Dainippon Ink and Chemicals Inc.); Bisphenol novolac type epoxy resin, such as NC-3000P (manufactured by Nippon Kayaku Co., Ltd.); and naphthol novolac type epoxy resin, such as ESN-165S (manufactured by Tohto Kasei Co., Ltd.) .

Examples of alicyclic epoxy compounds suitable for the synthesis of some resins include, but are not limited to, polyglycidyl ethers of polyols with at least one alicyclic ring and by epoxidation of compounds containing cyclohexene rings or cyclopentene rings The obtained epoxycyclohexane or epoxycyclopentene-containing compound. Specific examples include hydrogenated bisphenol A diglycidyl ether, 3,4-epoxycyclohexanecarboxylic acid 3,4-epoxycyclohexyl methyl ester, cyclohexyl-3,4-epoxy-1-methyl ring Hexanecarboxylic acid 3,4-epoxy-1-methyl ester, 6-methyl-3,4-epoxycyclohexylmethyl-6-methyl-3,4-epoxy-cyclohexanecarboxylic acid Ester, 3,4-epoxy-3-methylcyclohexanecarboxylic acid 3,4-epoxy-3-methylcyclohexylmethyl ester, 3,4-epoxy-5-methylcyclohexane Formic acid-3,4-epoxy-5-methylcyclohexyl methyl ester, 2-(3,4-epoxycyclohexyl-5,5-spiro-3,4-epoxy)cyclohexane-m Dioxane, bis(3,4-epoxycyclohexylmethyl) adipate, 3,4-epoxy-6-methylcyclohexyl formate, methylenebis(3,4-epoxy (Cyclohexane), dicyclopentadiene diepoxide, ethylidene bis(3,4-epoxycyclohexanecarboxylate), dioctylepoxyhexahydrophthalate and Epoxy hexahydrophthalate di-2-ethylhexyl ester.

Some of these alicyclic epoxy resins are commercially available as: UVR-6100, UVR-6105, UVR-6110, UVR-6128 and UVR-6200 (products of Dow Corporation); CELLOXIDE 2021, CELLOXIDE 2021P, CELLOXIDE 2081, CELLOXIDE 2083, CELLOXIDE 2085, CELLOXIDE 2000, CELLOXIDE 3000, CYCLMER A200, CYCLMER M100, CYCLMER M101, EPOLEAD GT-301, EPOLEAD GT-302, EPOLEAD 401, EPOLEAD 403, ETHB and EPOLEADHD 300 (products of Daicel Chemical Industries, Ltd.) ); KRM-2110 and KRM-2199 (products of ADEKA Corporation).

In addition to the resin, the curable composition may also include a free radical initiator (generated by heat or UV) and a curing agent. Curing can be done by heat or UV mechanism or both. In embodiments, latent epoxy-curing agents can also be used in the presence of epoxide rings.

Suitable thermal free radical initiators include, for example, organic peroxides and azo compounds known in the art. Examples include: azo free radical initiators such as AIBN (azobisisobutyronitrile), 2,2'-azobis(4-methoxy-2,4-dimethylvaleronitrile), 2,2 '-Azobis(2,4-dimethylvaleronitrile), 2,2'-Azobis(2-ethyl propionate), 2,2'-Azobis(2-methylbutane Nitrile), 1,11-azobis (cyclohexane-1-carbonitrile), 2,2'-azobis[N-(2-propenyl)-2-methylpropionamide]; dioxane Radical peroxide radical initiators, such as 1,1-di-(butylperoxy-3,3,5-trimethylcyclohexane); alkyl perester radical initiators, such as TBPEH ( Tert-butyl 2-ethylhexanoate); diacyl peroxide free radical initiators, such as benzoyl peroxide; peroxydicarbonate free radical initiators, such as ethylhexyl percarbonate ; Ketone peroxide initiators, such as methyl ethyl ketone peroxide, bis (third butyl peroxide) diisopropylbenzene, third butyl perbenzoate, peroxy neodecanoic acid Tributyl ester and its combination.

Other examples of organic peroxide radical initiators include: dilauryl peroxide, 2,2-bis(4,4-bis(third butylperoxy)cyclohexyl)propane, di(third Butyl peroxyisopropyl)benzene, bis(4-tert-butylcyclohexyl) peroxydicarbonate, behenyl peroxydicarbonate, dimyristyl peroxydicarbonate, 2,3 -Dimethyl-2,3-diphenylbutane, bisisophenylpropyl peroxide, dibenzoyl peroxide, diisopropyl peroxydicarbonate, monoperoxymaleic acid Third butyl ester, 2,5-dimethyl-2,5-di(third butylperoxy) hexane, third butyl carbonate 2-ethylhexyl carbonate, peroxy-2 -Third amyl ethylhexanoate, third amyl peroxypivalate, third amyl peroxycarbonate 2-ethylhexyl ester, 2,5-dimethyl-2,5-bis(2 -Ethylhexylperoxy)hexane, 2,5-dimethyl-2,5-di(third butylperoxy)hex-3, bis(3-methoxyperoxydicarbonate) Butyl) ester, diisobutylamide peroxide, tributyl peroxy-2-ethylhexanoate (Trigonox 21 S), 1,1-di(third butylperoxy) cyclohexane, Third butyl peroxyneodecanoate, third butyl peroxypivalate, third butyl peroxyneoheptanoate, third butyl peroxydiethyl acetate, 1,1-di (third (Butylperoxy)-3,3,5-trimethylcyclohexane, 3,6,9-triethyl-3,6,9-trimethyl-1,4,7-triperoxynon Alkanes, bis(3,5,5-trimethylhexyl) peroxide, hexanoic acid, tert-butylperoxy-3,5,5-trimethyl, peroxy-2-ethylhexyl Acid 1,1,3,3-tetramethylbutyl ester, peroxyneodecanoic acid 1,1,3,3-tetramethylbutyl ester, caproic acid third butyl peroxy-3,5,5- Trimethyl ester, cumyl peroxyneodecanoate, di-tert-butyl peroxide, tert-butyl peroxyisopropyl carbonate, tert-butyl peroxybenzoate, diperoxydicarbonate (2-ethylhexyl) ester, third butyl peroxyacetate, isopropyl cumyl hydroperoxide and third butyl cumyl peroxide.

Examples of suitable epoxy-based curing agents include (but are not limited to) Ajicure series hardeners from Ajinomoto Fine-Techno Co., Inc.; Amicure series hardeners from Air products and JERCURE™ products from Mitsubushi Chemical . These curing agents or hardeners are used in an amount of about 1% to about 50% by weight of the total composition, more preferably about 5% to about 20% by weight of the total composition.

The curable composition may contain another component capable of photopolymerization, such as a vinyl ether compound, as necessary. In addition, the curable composition may further include additives, resin components, and the like to improve or modify properties such as the following: flowability, distribution or printing properties, storage properties, curing properties, and physical properties after curing.

The composition may contain various other compounds as needed, such as organic or inorganic fillers, shakers, silane coupling agents, diluents, modifiers, colorants (such as pigments and dyes), surfactants, preservatives, stabilizers , Plasticizers, lubricants, defoamers, leveling agents and the like; however, they are not limited to these compounds. In detail, the composition may include additives selected from organic or inorganic fillers, shakers and silane coupling agents. These compounds may be present in an amount of about 0.1% to about 50% by weight of the total composition, more preferably about 2% to about 10% by weight of the total composition.

Fillers can include, but are not limited to, inorganic fillers such as silica, diatomaceous earth, alumina, zinc oxide, iron oxide, magnesium oxide, tin oxide, titanium oxide, magnesium hydroxide, aluminum hydroxide, magnesium carbonate, Barium sulfate, gypsum, calcium silicate, talc, glass beads, sericite activated clay, bentonite, aluminum nitride, silicon nitride, and the like; also organic fillers, such as poly (meth) methacrylate 、Polymethacrylate (ethyl), polymethacrylate (propyl), polymethacrylate (butyl), butylacrylate-methacrylic acid-methacrylic acid (meth)ester copolymer , Polyacrylonitrile, polystyrene, polybutadiene, polypentadiene, polyisoprene, polyisopropylene and the like. These can be used alone or in combination. These fillers may be present in an amount of about 1% to about 80% by weight of the total composition, more preferably about 5% to about 30% by weight.

Shaking agents may include, but are not limited to, talc, fumed silica, finely processed surface-treated calcium carbonate, fine-grained alumina, slab-shaped alumina; layered compounds, such as montmorillonite; needle-shaped compounds, such as boric acid Aluminum whiskers; and their analogs. Among them, talc, fumed silica and fine alumina are especially needed. These agents may be present in an amount of about 1% to about 50% by weight of the total composition, such as about 1% to about 30% by weight.

Silane coupling agents may include (but are not limited to) ɣ-aminopropyltriethoxysilane, ɣ-mercaptopropyltrimethoxysilane, ɣ-methacryloxypropyltrimethoxysilane, ɣ-shrink Glyceryloxypropyltrimethoxysilane and its analogs.

The curable composition can be obtained by mixing various ingredients by means of, for example, a mixer (such as a mixer with a stirring blade) and a three-roll mill. When the composition is liquid at ambient temperature, it has a viscosity of (for example, 200 to 400 Pa-s at a shear rate of 1.5 s-1 (at 25° C.), and simple distribution can be achieved.

According to the present invention, the method for synthesizing the star polymer additive thus disclosed includes: providing (meth)acrylate (such as tertiary butyl acrylate); injecting an initiator (such as tertiary butyl α-bromoisobutyrate); Injection of ligand (such as ginseng [2-(dimethylamino)ethyl]amine); addition of (meth)acrylate (such as n-butyl acrylate dissolved in acetonitrile); addition of 1,6-hexanedi Alcohol diacrylate and additional ligands; and isolated star polymer.

One aspect of the present invention includes a method of imparting improved viscosity drop resistance to a curable composition. The method includes the following steps: providing a curable resin selected from epoxy functional resin, (meth)acrylate functional resin, vinyl ether functional resin, vinyl ester functional resin, oxetane Alkane functional resin, cyanate ester functional resin, maleimide functional resin, nadi amide imide functional resin, itaconic amide imide functional resin or any two or more of them A mixture; providing a curing agent; adding an expandable viscosity modifier additive, compared to a curable composition without additives, the expandable viscosity modifier additive provides at least from the first lower temperature condition to the second higher temperature condition 2 times improved resistance to sudden drop in viscosity and volume expansion with increasing temperature. Compared to curable compositions without additives, swellable viscosity modifier additives provide a greater viscosity index, in some cases, an order of magnitude or two orders of magnitude. An improved sudden drop in viscosity can be observed in the temperature range of about 25°C to Tonset, depending on the nature and properties of the reactive ingredients in the composition. In most cases, Tonset can be about 65°C. Examples

The examples provided below present more details of the objectives, features and advantages of the present invention, but are not intended to be limiting.

表 1 In Table 1, various formulations are evaluated to test the viscosity modification properties of certain exemplary additives.

Table 1

In Table 1, Formulation A is a curable epoxy-functionalized resin system used as a control. Formulation A consists of two parts (about 66%) YL980 (from Mitsubishi Chemical, Chiyoda, Tokyo, Japan) and one part (about 33%) from Asahi Kasei's hardener HXA5926 (Chiyoda, Tokyo, Japan). YL980 is a bisphenol A type liquid epoxy resin with a total chlorine (CL) content of less than 300 ppm.

Formulations B, C, D, and E represent the percentage change of the star polymer additive included with the control epoxy functional resin system.

表 2 As explained in Figure 1 and Table 2 below, the sudden drop in viscosity of the curable epoxy-functionalized resin is improved by the additives of the present invention compared to the curable control epoxy-functionalized resin system without additives. An optical rheometer from Anton Paar GmbH of Germany was used to measure the viscosity at 25°C and 65°C. In detail, the MCR 301 and MCR 302 type rheometers provide viscosity measurements through controlled compression of the formulation.

Table 2

The viscosity index in Table 2 is the ratio calculated by dividing the Pascal second ("Pa-s") value at 65°C by the Pa-s value at 25°C.

As depicted in Figure 1 and Table 2, each of the tested samples (B, C, D, and E) had a higher viscosity index than the control without additives. Formulation C corresponding to 1.5% of the star polymer additive has the highest viscosity index of 0.932.

表 3 As illustrated in Table 3 below, the percentage viscosity index increase for each of the tested formulations caused a 10-fold, 30-fold, and 20-fold increase compared to the control, respectively.

Table 3

For formulations B, C, D and E, the viscosity increases with increasing temperature. This behavior is very different from the control system and the typical curing system, where the resin viscosity initially decreases when heat is applied and continues to decrease through the maximum flow area. Examples - Star polymers and synthesis

The star polymer can be synthesized in a container, such as a 250 ml four neck round bottom flask, which optionally contains a copper mesh, mechanical stirrer, condenser, additional funnel, and rubber septum. The procedures used to synthesize star polymers include some or all of the following steps.

Pre-treat the copper mesh with 0.1 N hydrochloric acid aqueous solution and rinse the copper mesh with acetone. A certain amount of acetonitrile (eg, 13 g) and (meth)acrylate, such as tert-butyl acrylate (eg, 12.80 g, 100 mmol) are added. Add copper (II) bromide (for example, 0.013 g, 0.05 mmol, or acetonitrile containing CuBr ₂ stock solution). The mixture is flushed with nitrogen for a period such as 30 minutes. The mixture was heated to approximately 45°C. Inject the initiator α-bromoisobutyrate tert-butyl ester (eg, 1.115 g, 5 mmol) and ligand Me ₆ TREN (eg, 0.12 g, 0.50 mmol, or acetonitrile with stock solution) via a closed syringe To the mixture.

The reaction can be monitored with ¹ H NMR until t-BuA conversion is greater than 85%. In an embodiment, the t-BuA conversion takes about two hours.

Referring to FIG. 2, size exclusion chromatography (specifically, GPC) can be used to test molecular weight and polydispersity index ("PDI"). After the test, in the examples, the molecular weight of the star polymer was about 7.5 kDa. In addition, the molecular dispersion is narrow because the PDI is only 1.02.

The procedure for synthesizing the star polymer may further include the steps of: adding a (meth)acrylic acid ester (such as n-butyl acrylate (eg, 51.2 g, to a 200 ml additional funnel purged with nitrogen (N ₂ ) 400 mmol)) of acetonitrile (for example, 52 g). The reaction was monitored with ¹ H NMR until the n-BuA conversion was greater than 85%, which can take approximately three hours. Similarly, the molecular weight and PDI can be checked by GPC. In the embodiment, using the procedure described above, the PDI is excellent at only 1.03.

The procedure for synthesizing the star polymer may further include the following steps: add 1,6-hexanediol diacrylate ("HDDA") to a 60 ml extra funnel purged with nitrogen (N ₂ ) (eg, 7.49 Grams, 35 mmol in, for example, acetonitrile (13g)). Additional ligands such as Me ₆ TREN (eg, 0.12 g, 0.50 mmol, or acetonitrile with stock solution) can be injected. ¹ H NMR can be used to monitor the subsequent reaction until the n-BuA conversion is greater than 95%, which can take approximately three hours.

Referring to Figure 3, molecular weight and PDI can be checked by GPC. In the exemplary embodiment, the molecular weight was found to be about 31 kDa and the PDI was about 1.15.

The procedure for synthesizing the star polymer may further include the following steps: removing the Cu(0) net from the container, and applying a p-toluenesulfonic acid monohydrate ("p-TSA H ₂ O") acetonitrile solution (eg, about 2 g) Add to the mixture. In an embodiment, the mixture can be refluxed for about six hours. After refluxing, the star copolymer containing polybutyl acrylate was converted to polyacrylic acid, which can be confirmed by the disappearance of the third butyl group by ¹³ C NMR.

The procedure for synthesizing the star polymer may further include the step of precipitating the resulting star polymer from the acetonitrile solution by a ratio of methanol and water (“MeOH/H ₂ O”) of, for example, 10:1. In an embodiment, additionally or alternatively, the star polymer may be precipitated by fractionation with tetrahydrofuran and methanol ("THF/MeOH"), washed with MeOH and dried in vacuum.

Most of the arm copolymer can be removed after passing through the fractional precipitation method twice. In a preferred embodiment, almost 99% star polymer is obtained.

Referring to FIG. 4, according to ¹³ C NMR spectrum, it was found that the third butyl group was removed by acid treatment. Example - Hyperbranched polymer

Referring to FIG. 5, in one aspect of the present invention, a hyperbranched polymer (which includes the comb polymer additive of the present invention) is synthesized based on a polyamide structure. In the examples, different amines and acids were introduced into the system to check the effect of anti-viscosity droop. An example of a possible synthesis route for hyperbranched polymers is further described below.

Trimer acid (Autrex 1006, three functional groups from Autrex Industrial (Pty) Ltd., Western Cape, South Africa) (2.10 g; 10 mol), p-phenylene diamine (1.08 g; 10 mmol) , Pyridine (7.5 mL), triphenyl phosphite (7.82 ml; 130 mmol) and 80 mL N-methyl-2-pyrrolidone ("NMP") were added to a 250 mL three-necked flask with nitrogen (N ₂ )protection. Next, with the oil bath, the reaction was heated to 180°C. In the examples, the reaction was allowed to continue for about two hours.

The resulting product can be precipitated in methanol. The product was washed with more methanol and dried in vacuum. The product was confirmed by GPC.

表 4 The different amide polymers synthesized by this method are illustrated in Table 4. Most polymers exhibit a molecular weight of about 13 kDa to about 30 kDa.

Table 4

Although the present invention has been described and described with respect to specific embodiments thereof, those of ordinary skill in the art should understand that various modifications can be made to the present invention without departing from the spirit and scope of the present invention.

FIG. 1 is an exemplary graphical representation of several curable resin systems containing additives compared to curable resin systems without additives.

FIG. 2 is an illustrative diagram of one of the block copolymers synthesized for forming various additives.

FIG. 3 is an illustrative diagram of one of synthetic star copolymer additives.

FIG. 4 is an exemplary illustration of the results of gel permeation chromatography ("GPC") of star copolymer additives and ¹³ C nuclear magnetic resonance ("NMR") spectroscopy spectra.

FIG. 5 is an illustrative diagram of one synthetic hyperbranched polymer additive.

Claims (29)

A curable composition comprising: a curable epoxy-functionalized resin based on bisphenol A, bisphenol F, bisphenol S, phenol-novolac, dicyclopentadiene, naphthalene or any two or More types of mixtures; Polyamide additives for curable compositions. The volume of the curable composition expands with increasing temperature. The additive contains the following structure:

Where: R is an aliphatic alkyl chain; and n is 1 to 50; and a curing agent; wherein relative to the curable composition without the additive, the additive provides the curable composition with a temperature of 25°C to 65°C 1 to 100 times improved resistance to sudden drop in viscosity. The curable composition according to claim 1, wherein R is an aliphatic alkyl chain containing an oxygen atom. The curable composition according to claim 1, wherein R is an aliphatic alkyl chain containing a sulfur atom. The curable composition according to claim 1, wherein R is an aliphatic alkyl chain containing a nitrogen atom. The curable composition according to claim 1, wherein R is an aromatic ring. A curable composition comprising: Curable epoxy-functional resin based on bisphenol A, bisphenol F, bisphenol S, phenol-novolac, dicyclopentadiene, naphthalene or a mixture of any two or more thereof; Star polymer additive, which contains: The core formed by the network structure of the cross-linked polymer; and A plurality of linear polymer chains extending from the core; Wherein the molecular weight of the core is 10 to 20 times greater than the molecular weight of the plurality of linear polymer chains; Wherein compared to the curable composition without the additive, the star polymer additive provides 1 to 100 times improved resistance to sudden drop in viscosity at 25°C to 65°C; Where the volume of the star polymer additive expands with increasing temperature; and Hardener. The curable composition according to claim 6, wherein the plurality of polymer chains are acrylate polymer chains. The curable composition of claim 7, wherein the acrylate polymer chain is connected to the core by reaction with α-bromo-ester. The curable composition according to claim 6, wherein the core is formed by copolymerizing a block copolymer linked by P-1,6-hexanediol diacrylate-P', and wherein P and P'are each The copolymers can be the same or different. The curable composition according to claim 6, wherein the end of the at least one linear polymer chain farthest from the core is capable of hydrogen bonding via a hydroxyl group. The curable composition according to claim 6, wherein the end of the at least one linear polymer chain closest to the core is additionally bonded to the core by hydrogen bonding. A curable composition comprising: Curable epoxy-functional resin based on bisphenol A, bisphenol F, bisphenol S, phenol-novolac, dicyclopentadiene, naphthalene or a mixture of any two or more thereof; Comb-shaped polymer additive consisting of a main chain with two or more three-way branch points and a linear side chain extending from each branch point; and Hardener; Wherein, compared to the curable composition without the additive, the comb polymer additive provides the curable composition with an improved viscosity drop resistance of 1 to 100 times from 25°C to 65°C; and The volume of the comb polymer additive expands with increasing temperature. The curable composition according to claim 12, wherein the comb polymer comprises the following structure:

Where: X is 1-20. The curable composition according to claim 12, wherein at least two linear side chains extending from different branch points are the same. The curable composition according to claim 12, wherein all the linear side chains extending from the branch points are the same. The curable composition according to claim 12, wherein at least two linear side chains extending from different branch points are different. The curable composition of claim 12, wherein all of the linear side chains extending from the branch points are different. A curable composition comprising: Curable epoxy-functional resin based on bisphenol A, bisphenol F, bisphenol S, phenol-novolac, dicyclopentadiene, naphthalene or a mixture of any two or more thereof; Repeated branched dendrimer additives; and Hardener; Compared with the curable composition without the additive, the dendritic polymer additive provides 1 to 100 times improved resistance to sudden drop in viscosity at 25°C to 65°C; and The volume of the dendrimer additive expands with increasing temperature. The curable composition according to claim 18, wherein the dendrimer additive has the following structure:

. The curable composition of claim 18, wherein the dendrimer additive has a molecular weight between about 10 and 250 kDa. A curable sealant composition, comprising: Curable epoxy-functional resin based on bisphenol A, bisphenol F, bisphenol S, phenol-novolac, dicyclopentadiene, naphthalene or a mixture of any two or more thereof; Additives, the volume of the additives expands with increasing temperature; and Hardener; Compared with the curable composition without the additive, the additive provides the curable composition with 1 to 100 times improved resistance to sudden viscosity drop in the temperature range of 25°C to 65°C. The curable composition of claim 21, wherein the additive is about 0.1 to about 20% by weight of the curable composition. The curable composition of claim 21, wherein the additive is about 0.1 to about 10% by weight of the curable composition. The curable composition of claim 21, wherein the additive is about 0.1 to about 5% by weight of the curable composition. The curable composition according to claim 21, further comprising one or more of the following: filler, toughening agent, toughening agent, phenol-novolac hardener, epoxy curing catalyst, curing agent or adhesion promotion Agent. A method for synthesizing an additive for a curable drop injection (ODF) sealant composition, which comprises: Provide the first (meth)acrylate and the first ligand to form the core network structure of the cross-linked polymer; Adding a second (meth)acrylate and a second ligand to the core network structure to form a plurality of linear polymer chains extending from the core network structure; and The resulting star polymer is isolated. The method of claim 26, wherein the conversion of the first (meth)acrylate to the core network structure is greater than 85%. The method of claim 26, wherein the conversion of the second (meth)acrylate to the plurality of linear polymer chains is greater than 85%. A method for imparting improved viscosity drop resistance to a curable composition includes the following steps: Provide curable epoxy-functional resins based on bisphenol A, bisphenol F, bisphenol S, phenol-novolac, dicyclopentadiene, naphthalene or any two or More kinds of mixtures; Provide curing agent; and Add expandable viscosity modifier additives; Wherein the swellable viscosity modifier additive provides 1 to 100 times improved viscosity sag resistance compared to the curable composition without the additive; and The volume of the expandable viscosity modifier additive expands with increasing temperature.

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