TW200838940A - Room-temperature curable polyorganosiloxane composition and flat panel display device - Google Patents

Abstract

To provide a room-temperature curable polyorganosiloxane composition having a low viscosity before curing, having characteristics of exhibiting high adhesiveness after curing to cause excellent peelability by the balance thereof, and also having good preservability.; The room-temperature curable polyorganosiloxane composition comprises (A) a polyorganosiloxane having both terminals terminated with trialkoxysilyl groups, (B) a polyorganosiloxane comprising a polyorganosiloxane having both terminals terminated with dialkoxymonoorganosilyl groups, c a one-terminal-triorganooxy-polyorganosiloxane curing agent represented by formula (1), (D) an organotrialkoxysilane represented by formula (2), (E) silica powder and (F) a titanium chelate catalyst as essential components.

Description

200838940 IX. INSTRUCTIONS OF THE INVENTION [Technical Field] The present invention relates to an organopolyoxane composition composed of a room temperature hardened polyoxyalkylene oxide, and more specifically relates to a composition before hardening. The viscosity and the physical properties after hardening are good, in particular, a room temperature curable organopolysiloxane composition having a high elongation and imparting a good releasability from a contact surface with a substrate, and having good storage properties, and the use of the composition A flat panel display device as an electrode coating material. [Prior Art] The composition of the curable organopolyoxane which is crosslinked by moisture is excellent in adhesion and electrical properties, and can be used in sealing materials for building materials, electrical and electronic fields, and conveyors. Various fields such as bonding agents. In the field of electrical and electronic applications, the curable organopolyoxane composition is often used for coating of an electrode or a circuit board, and it is required that the composition before curing has a low viscosity and the bonding property between the cured product and the substrate after curing is good. However, in recent years, in the field of electrode coating of LCD panels, it is necessary to peel the cured product from the joint surface with the substrate due to repair of the completed LCD panel, etc., in this case, it is required that no hardened material remains on the surface of the substrate. The interface is peeled off. In order to solve this problem, JP-A-2005-082734 (Patent Document 1) uses an organopolysiloxane having a terminal blocked by a dialkoxy monoorganoalkylene group or both ends blocked by a trialkoxyalkylene group. The organic polyoxane, as a matrix polymer, is treated as a surface agent with a non-sterol group, a trialkoxy group and a dialkoxy group as a chelating agent. The combination of ceria in 200838940, alkoxysilane of a bifunctional group as a crosslinking agent, a partially hydrolyzed condensate thereof, and a titanium chimeric catalyst is attempted to coexist both adhesion and releasability. However, when the inventors of the present invention conducted the same experiment, according to the technique of Patent Document 1, it is possible to obtain a composition having a certain degree of adhesion and releasability, but it is confirmed that the surface of the cured product does not contain a sterol group or a trioxane. The organopolyoxyalkylene of the oxy group and the dialkoxy group bleed out from the hardened material. Further, the alkoxysilane or the partially hydrolyzed condensate thereof having a bifunctional group as a crosslinking agent has a large crosslinking density, which is low in elongation, and the cured product is broken at the time of peeling, and the peeling property cannot be satisfied. [Problem to be Solved by the Invention] In view of the above, the present invention provides a low viscosity before curing, and is excellent in physical properties after curing. It is a room-temperature-curable organopolyoxane composition which is highly stretched and imparts a good releasability from a contact surface with a substrate, and which has good preservability, and a flat panel display using the composition as an electrode coating material. The device is for the purpose. [Means for Solving the Problem] In order to solve the above problems, the inventors of the present invention proposed to use an organopolyoxane whose both ends are blocked by a dialkoxy monoorganoalkylene group and the above-mentioned Japanese Patent Application No. 2006-05 5 805 / or an organopolysiloxane having a terminal blocked by a trialkoxysulfonylalkyl-6 - 200838940 as a matrix polymer, by using it as an organopolyoxyalkylene hardener having a triorganooxy group at one end The combination of the surface treated cerium oxide and the titanium chimeric catalyst of the chelating agent can improve adhesion and peelability. According to this proposal, it is possible to provide a composition having a low viscosity before curing, and having good physical properties after curing, and in particular, a room temperature-curable organic polycondensation of a cured product which is highly stretched and imparts excellent releasability from a contact surface with a substrate. An oxane composition, but it is desirable to further improve storage stability. Therefore, the present inventors have further carried out the review and found that the organopolysiloxane having both ends blocked by a trialkoxyalkylene group and the organic polycondensation at both ends thereof blocked by a dialkoxymonoorganoalkylene group are found. Oxane, which is a matrix polymer and which combines a single-end triorganooxyorganopolyoxyalkylene oxide and an organotrialkoxydecane as a hardener, is very effective, and thus the present invention has been completed. That is, the present invention provides an organopolyoxane characterized by blocking (A) 25 ° C viscosity of 0.1 to 1,000 Pa · s at both ends by a trialkoxyalkylene group: 5 to 95% by mass; (B) an organic polyoxane having a viscosity at 25 ° C of 0.1 to 1,000 Pa·s blocked by a dialkoxy monoorganoalkylene group: 95 to 5 mass%; For the alkane 100 parts by mass; (C) The following general formula (1) [Chemical 1] R1 R1—Si-X- R1 , R 2 , I • Si Ο · R 2 OR 3 Si—X—Si—OR3

I

R2 Jn R2 OR3 (wherein, R1, R2 and R3 are monovalent saturated hydrocarbon groups, X is an oxygen atom • Ί - 200838940 or a divalent hydrocarbon group, and η means that the viscosity at 25 ° C is 0.005 to 100 Pa·s is preferably lower. a single-end triorganooxyorganopolyoxyalkylene hardener represented by a positive number of the components (A) and (B) used: 1 to 50 parts by mass; (D) the following general formula (2) [ 2] OR5 R4—Si—OR5 (2) • (W5 (wherein R 4 is a monovalent hydrocarbon group, and R 5 is an alkyl group substituted by an alkyl group or an alkoxy group): an organotrialkoxy decane represented by 0.2~ 50 parts by mass; (E) cerium oxide powder having a specific surface area of 50 m 2 /g or more: 1 to 50 parts by mass; and (F ) titanium tong catalyst catalyst · 0.1 to 15 parts by mass; A composition of a curable organopolyoxane and a flat panel display device using the composition as an electrode coating material. [Effects of the Invention] - In the present invention, (A) component and (B) component are used. The terminal 3 functional group and the bifunctional group polymer were found to have moderate rubber strength by blending these with a monofunctional 3-functional organopolyoxane. The agent (C), the organotrialkoxysilane crosslinker (D) and the cerium oxide powder (E) have a low viscosity before curing, and a high adhesion after hardening, due to the balance of these A cured product which is excellent in releasability and has good preservability -8 - 200838940. [Embodiment] The organopolysiloxane of the components (A) and (B) used in the present invention is a matrix of the present composition. a polymer, compounding (A) an organopolyoxyalkylene blocked at both ends by a trialkoxyalkylene group and (B) an organopolyoxane blocked at both ends by a dialkoxy monoorganoalkylene group, (A) In the case of 5 to 95% by mass of the component, the component (B) is 95 to 5% by mass, and more preferably 10 to 90% by mass of the component (A), and the component (B) is 90 to 10% by mass. When the amount of the component (A) is less than 5% by mass, the interfacial peelability from the substrate is poor, and when it exceeds 95% by mass, the elongation is lowered. Such a method for producing an organopolysiloxane has been widely known, for example, to have hydrogen at both ends of a molecular chain. a polyalkylidene oxane with a decyl group and a tetraalkoxy decane or an alkyltrialkoxy decane A method of performing a condensation reaction, a method of performing an addition reaction of a polydiorganomethoxy alkane having an alkenylalkyl group at both ends of a molecular chain with a trialkoxydecane or an alkyldialkoxydecane. (A) The component (B) is not particularly limited as long as it is a terminal organic structure, and is usually a compound which bonds to a ruthenium atom, such as an alkyl group, if it is cured by a linear organopolysiloxane or the like. a monovalent hydrocarbon group having 1 to 8 carbon atoms such as a cycloalkyl group, an alkenyl group or an aromatic group, and a halogenated hydrocarbon group such as a chloromethyl group or a trifluoromethyl group in which a part or all of the hydrogen atoms of the monovalent hydrocarbon group are substituted with a halogen atom. The viscosity of the component (A) at 25 ° C is from 0·1 to 1,000,000 Pa·s', which is preferably 2 to 100 Pa·s. When it is less than 0.1 Pa·s, the rubber is low and -9 - 200838940 is brittle and the interface peeling property is deteriorated. Moreover, when it is higher than l, 〇〇〇Pa · s, it becomes a high viscosity, and workability deteriorates. Moreover, in the present invention, the viscosity is a viscosity 根据 according to a rotational viscometer. The viscosity of the component (B) at 25 ° C is 〇·1 〜1, 〇〇〇Pa· s, which is preferably 0.2 to 100 Pa·s. When it is less than 0.1 Pa · s, the rubber becomes brittle due to low elongation, and the interfacial peelability is deteriorated. Moreover, when it is higher than l, 〇〇〇Pa · s, it becomes a high viscosity, and workability deteriorates.

In this case, it is more preferable to use the organopolyoxane represented by the following formula (4) using the following formula (3) or (B) as the component (A). [Chemical 3] OR11 r R12

Rn〇-Si-〇- I OR11 OR13R14 — Si-O-I OR13 OR11 -Si-OR11 -Si—〇 I I ^R12 Λ OR11

rR15, I -Si—O-I OR13 •Si-R14 V.R15 Λ OR13 (3) (4)

In this case, R11 and R13 are the same or different alkyl groups having 1 to 4 carbon atoms, and particularly preferably a methyl group or an ethyl group. R12, R14, and Rl5 are the same or different monovalent hydrocarbon groups such as a methyl group having 1 to 8 carbon atoms, an aromatic group such as a phenyl group, or the like, and 1 hydrogen atom of these monovalent hydrocarbon groups. The above halogenated monovalent hydrocarbon group substituted by a halogen atom, particularly R14, is preferred as a hospital base. a is such that the viscosity of the organic polyoxane of the formula (3) at 25 ° C becomes 〇·1 to l,000 Pa · s, and b is such that the viscosity of the organic polyoxyalkylene of the formula (4) becomes 25 ° C. 〇. 1~1, 〇〇〇pa · s number. Further, the viscosity of the component (A) and the component (B)' may be higher or may be the same, and it is preferable that the component (B) has a high viscosity. The single-end triorganooxyorganopolysiloxane of the component (C) used in the present invention is an improvement of the elongation of the cured product by the following formula (1): 7f\° [Chemical 4] R1 R1 - Si- X-R1

,R2 I Si-O ^R2 R2 OR3 -Si-X-Si-〇R3 R2 OR3 (1)

(wherein 'Ri' R2 and R3 are a monovalent saturated hydrocarbon group, X is an oxygen atom or a divalent hydrocarbon group, and n is a positive number such that the viscosity at 25 ° C becomes 0.005 to 100 Pa · s, preferably such that it is not used. The positive number of the (A) and (B) components. Here, as the monovalent saturated hydrocarbon group, an alkyl group having 1 to 4 carbon atoms is preferable as a divalent hydrocarbon group, for example, a carbon number! ~4 alkenyl and the like. It is preferred that the side chain is similar to the components of (A) and (B). Further, the viscosity at 25 °C of the component (C) is preferably at least lower than the viscosity of any of the components (A) and (B). More preferably, the viscosity is lower than the components (A) and (B). When the viscosity of the component (C) is higher than the components (A) and (B), the viscosity becomes high, and the workability may be deteriorated. Specifically, the viscosity of the component (C) is preferably 0.005 to 100 Pa·s, particularly 0.01 to 1 OPa · s. The component (C) is used as a crosslinking agent, and the components (a) and (B) are For a total of 100 parts by mass, 1 to 50 parts by mass is used. When the amount is less than 1 part by mass, sufficient adhesion and elongation cannot be obtained. When the amount is more than 50 parts by mass, the rubber strength is lowered and the interfacial peelability is lowered. More preferably 3 -11 - 200838940 ~ 30 parts by mass. The organotrialkoxydecane of the component (D) used in the present invention is also represented by the following formula (2) as a crosslinking agent. OR5 R4 — Si—OR5 (2) OR5 (wherein R 4 is a monovalent hydrocarbon group such as an alkyl group, an alkenyl group (vinyl group, etc.), an aromatic group (phenyl group, etc.), and R 5 is an alkyl group or an alkane. An oxy-substituted alkyl group (methoxymethyl, methoxyethyl, ethoxymethyl, ethoxyethyl))c Here, as a monovalent hydrocarbon group of R4, a carbon number of 1 to 20 Preferably, a saturated hydrocarbon group or an unsaturated hydrocarbon group is preferred. More preferably, it is an alkyl group having 5 to 12 carbon atoms. R5 is an alkyl group or an alkoxy-substituted alkyl group having the same or different carbon number of 1 to 4, and particularly preferably a methyl group or an ethyl group. As the component (D), specifically, for example, methyltrimethoxydecane, propyltrimethoxydecane, hexyltrimethoxydecane, decyltrimethoxydecane, vinyltrimethoxydecane, phenyltrimethoxydecane, Methyl triethoxy decane, propyl triethoxy decane, hexyl triethoxy decane, decyl triethoxy decane, vinyl triethoxy decane, phenyl triethoxy decane, and the like. Here, in the case of using a dialkoxy decane or a monoalkoxy decane, sufficient preservability cannot be obtained. The component (D) is used in an amount of from 0.2 to 50 parts by mass based on 100 parts by mass of the components (A) and (B). When the amount is less than 0.2 parts by mass, sufficient preservability cannot be obtained. When the amount is more than 50 parts by mass, the crosslinking density is increased by -12 to 200838940, and the cured product becomes brittle and the peeling property is deteriorated. More preferably, it is 0.5 to 30 parts by mass. The cerium oxide of the component (E) used in the present invention is a cerium oxide powder having a specific surface area of 50 m 2 /g or more, such as an aerosol cerium oxide, a cerium oxide or a surface thereof, an organochloro decane or an organic polyoxygen oxychloride. A conventionally known treatment agent such as an alkane or an organopolyazane is subjected to surface treatment. Here, the specific surface area is based on the BET method. The component (E) is used in an amount of from 1 to 50 parts by mass, more preferably from 3 to 30 parts by mass, based on 100 parts by mass of the components (A) and (B). As the titanium clamp catalyst of the component (F) used in the present invention, for example, diisopropoxy bis(ethyl acetoxyacetate) titanium, diisopropoxy bis(ethyl methacrylate) titanium , various titanium clamps such as diisopropoxy bis(acetonitrile) titanium, dibutoxy bis(ethyl acetoxyacetate) titanium, dimethoxy bis(ethyl acetoxyacetate) titanium, and the like Compound. The component (F) is used in an amount of from 0.1 to 15 parts by mass, particularly from 0.3 to 10 parts by mass, based on 100 parts by mass of the components (A) and (B). The composition of the present invention is composed of the above components (A) to (F). In addition to the above components, inorganic particles such as quartz fine powder, carbon black, and calcium carbonate may be added as long as the object of the present invention is not impaired. A sputum agent, a hydrophobization agent, a thixotropic agent, a viscosity modifier, a fluidity adjuster, a pigment, an organic solvent, an antifungal agent, an antibacterial agent, an ultraviolet absorber, a heat resistance improver, a flame retardant, Various additives such as adhesion enhancers. In the composition of the present invention, the components (A) to (F) described above are generally used in a mixing machine, such as a Shinagawa mixer, a planetary mixer, or a jet mixer, and are preferably operated in a water-free state. It can be manufactured by kneading, and can be used for coating electrodes and circuit boards in the field of electric electronics, and the like, particularly for electrode coating of flat panel display (FPD) panels such as liquid crystal display (LCD) panels. For use in these applications, coating The thickness of the cloth is about 0.2 to 1.0 mm, and it can be used by being placed in the atmosphere at room temperature, for example, by hardening under the conditions of so-called 23 ° C, 50% RH, and 24 hours. [Examples] Hereinafter, the present invention will be specifically described by way of Examples, but the present invention is not limited to the following Examples. Moreover, in the examples, parts are all parts by mass. Moreover, the viscosity indicates the enthalpy at 25 ° C as measured by a rotary viscometer. [Example 1] The polymer (A) was prepared (the both ends of the dealcoholization condensation reaction of polydimethyloxane having a hydroxyalkyl group at both ends of the molecular chain and tetramethoxydecane were blocked by a trimethoxydecyl group) Polydimethyl methoxy oxane (viscosity at 25 ° C is 1 Pa * s) 50 parts, polymer (B) (polydimethyl methoxy oxane and methyl trimethoxy group having hydroxy decyl group at both ends of the molecular chain) The decane is subjected to a dealcoholization condensation reaction, and the polydimethylsiloxane (the viscosity at 25 ° C is IPa · s) blocked by the methyl dimethoxy fluorenyl group is 50 parts, and the specific surface area according to the BET method is 200 m 2 . /g of dry cerium oxide (cerium oxide A) 10 parts, mixed under 15 (TC, 40mmHg under reduced pressure for 2 hours. After cooling to room temperature, add hardener (C) (single-terminal trimethoxy polydimethyl The oxirane (25 has a viscosity of 0.02 Pa.s)) 10 parts and 5 parts of an alkyltrialkoxydecane A (-14 - 200838940 methyltrimethoxydecane) were mixed at room temperature for 30 minutes. To the mixture, 2 parts of titanium clamp catalyst (F) (diisopropoxy bis(ethyl acetoxyacetate) titanium) was added, and the mixture was uniformly mixed under moisture resistance. [Example 2] 50 parts of the polymer (A) used in Example 1, formulated with polymer (B) 50 parts, cerium oxide A 10 parts, decompressed at 50 ° C, 4 〇 mmHg Bottom 'mix for 2 hours. After cooling to room temperature, add hardener (c) (single-terminal trimethoxypolydimethyloxane (viscosity of 0.02 Pa·s at 25 ° C)) 1 〇 and alkyl 5 parts of trialkoxydecane B (propyltrimethoxydecane), mixed for 30 minutes at room temperature. Add 2 parts of titanium clamp catalyst (F) to the mixture (diisopropoxy double (B) Ethyl thiol ethyl acetate.) Titanium) was mixed until uniform under moisture resistance. [Example 3] ^ Polymer (A) used in Example 1 50 parts, formulated polymer (B) 50 10 parts of cerium oxide A, 'mixed for 2 hours at 150 ° C, 40 mmHg under reduced pressure. After cooling to room temperature, add hardener (C) (single terminal 5 and dimethoxy polydimethyl sulphide (Viscosity at 25 ° C is 0.02 Pa·s)) 1 part by weight and 5 parts of alkyltrialkoxydecane C (hexyltrimethoxydecane), mixed at room temperature for 30 minutes. Add titanium clamp to the mixture. Compound catalyst (F) 2 parts (diisopropyl -15- 200838940 base bis(ethyl acetoxyacetate), mixed to homogeneity under moisture resistance. [Example 4] 50 parts of polymer (A) used in Example 1, compounding polymerization 50 parts of the substance (B) and 10 parts of cerium oxide A, mixed at 150 ° C under a reduced pressure of 40 mmHg for 2 hours. After cooling to room temperature, a hardener (C) (single-terminal trimethoxypolydimethyl hydrazine) was added. Oxygenane (viscosity of 0.02 Pa.s at 25 ° C)) 10 parts and 5 parts of alkyltrialkoxydecane D (decyltrimethoxydecane) were mixed at room temperature for 3 minutes. To the mixture, 2 parts of a titanium clamp catalyst (F) (diisopropoxybis(ethyl acetoxyacetate) titanium) was added, and the mixture was mixed until it was uniform under moisture. [Comparative Example 1] The composition was prepared in the same manner as in Example 1 except that 5 parts of the sulfhydryl sulphate A (methyltrimethoxy decane) were not prepared. [Comparative Example 2] In Example 1, the composition was adjusted in the same manner except that the curing agent (C) was not prepared. [Comparative Example 3] In Example 1, the same procedure was carried out except that 5 parts of dimethyldimethoxy sulfoxide was substituted for -16.200838940 alkyltrialkoxydecane A (methyltrimethoxydecane). Composition. [Comparative Example 4] In Example 1, a composition was prepared in the same manner except that 5 parts of a substituted alkyltrialkoxydecane A (methyltrimethoxydecane) was prepared by mixing trimethylmethoxydecane. φ For the composition obtained above, the initial viscosity and the viscosity after being placed in a thermostat bath at 70 ° C for 7 days in a polyethylene crucible were measured, and the viscosity from the initial viscosity to 7 days after the deposition was calculated. Increase the stickiness. The results are shown in Table 1. Further, a model frame having a thickness of 2 mm was placed on a glass plate and a glass epoxy plate, and the composition was poured thereon, and the cells were maintained at 23 ° C and 50% RH for 7 days to obtain a cured product having a thickness of 2 mm. Confirm the peeling rate from the interface of the glass plate. The results are shown in Table 1. -17- 200838940 [Table 1]

Composition amount (parts by mass) Example 1 Example 2 Example 3 Example 4 Comparative Example 1 Comparative Example 2 Comparative Example 3 Comparative Example 4 (A 戚Dimerization·ίΑ) 50 50 50 50 50 50 50 50 (B戚Mate polymer (Β) 50 50 50 50 50 50 50 50 (C minus hardener (C) 10 10 10 10 10 10 10 (D 戚 alkyl trialkoxy decane A 5 alkyl trialkoxy Decane B 5 alkyl trialkoxy decane C 5 alkyl trialkoxy decane D 5 comparative component dimethyl dimethoxy decane 5 trimethyl methoxy decane 5 (E) component oxidized stone eve A 10 10 10 10 10 10 10 10 (F 二 diisopropoxy bis(ethyl acetoxyacetate) titanium 2 2 2 2 2 2 2 2 Interfacial peeling rate (%) Glass plate 90 90 100 100 100 20 100 100 Glass Epoxy board 95 95 100 100 100 20 100 100 Initial viscosity (Pa · s) (X) 2.3 2.4 2.4 2.6 2.9 3.1 2.3 2.3 Viscosity after 7 days at 70 ° C (Pa · s) (Y) 2.3 2.4 2.5 2.7 5.0 3.2 3.6 4.2 Adhesion increase ratio (7)/(8) 1.00 1.00 1.04 1.04 1.72 1.03 1.57 1.83 -18-

Claims (1)

200838940 X. Patent Application No. 1 · A room temperature curable organopolyoxane composition characterized by: a (A) 25 ° C viscosity of 0.1 to 1,000 Pa · s at both ends of the trialkoxide Organic polyalkylene oxide blocked by alkyl group: 5 to 95% by mass; (B) Organic polycondensation at 25 ° C with a viscosity of 0.1 to 1,000 Pa · s at both ends blocked by a dialkoxy monoorganoalkylene group Hexane: 95 to 5 mass%; 100 parts by mass of the organic polyoxane formed; (C) the following general formula (1): R1 R1 - si-X - I R1 m r2 〇 R3 Si—Ο—Si—X~ Si—OR3 (1) ^R2 Jn R2 OR3 (wherein R1, R2 and R3 are monovalent saturated hydrocarbon groups, X is an oxygen atom or a divalent hydrocarbon group, and η represents a viscosity of 25 ° C a single-terminal triorganooxyorganopolyoxyalkylene hardener represented by a positive number of 0.005 to 100 Pa·s: 1 to 50 parts by mass; (D) the following general formula (2) [Chemical 2] OR5 R4-Si -〇R5 (2) I OR5 (wherein R4 is a monovalent hydrocarbon group, and R5 is an alkyl group or an alkoxy-substituted alkyl group) -19- 200838940 The organic trialkoxy decane represented by 0.2 to 50 parts by mass ; (E The cerium oxide powder having a specific surface area of 50 m 2 /g or more: 1 to 50 parts by mass; and (F) the titanium tongs catalyst: 0.1 to 15 parts by mass; is an essential component. 2. The room temperature curable organopolyoxane composition as claimed in claim </ RTI> wherein the n component of the component (C) is 25. (The viscosity of the single-end triorganooxyorganopolyoxyalkylene hardener of (:) is a positive number of 0.01 to 0.5 Pa·s. 室温3. The room temperature curable organopolysiloxane composition of the first aspect of the patent application is 'The R4 of the component (D) is an alkyl group having 5 to 5 carbon atoms; 4. A flat panel display device characterized by using room temperature hardenability as in the first, second or third aspect of the patent application. An organic polyoxane composition as an electrode coating material. -20- 200838940 无····························································································· , please reveal the chemical formula that best shows the characteristics of the invention.