TW200827407A - Addition reaction type polysiloxane series stripping agent combination and stripping film - Google Patents

Abstract

The topic of the present invention: under maintaining excellent stripping property of the stripping agent layer toward the adhesive layer, the adhesion of the stripping agent layer toward the substrate is simultaneously made excellent. Solution of the present invention is to provide an addition reaction type polysiloxane series stripping agent combination, which includes the addition reaction type polysiloxane resin, the branched organo-siloxane oligomer, crosslinking agent, and catalyst. The addition reaction type polysiloxane resin is e. g. the poly-organosiloxane with one molecule containing at least two alkenyl groups as the functional group; the branched organo-siloxane oligomer is the one using at least two alkenyl groups. In the above combination, the ratio of the number of alkenyl groups relative to the number of methyl groups is 0.02-0.08 (molar ratio).

Description

[Technical Field] The present invention relates to an addition reaction type polyoxygen-based release agent composition which suppresses release of a release agent from a substrate and which has excellent release properties, and a release sheet using the same . [Prior Art] The release sheet can be used for the protection of an adhesive for an adhesive article, for example, for the manufacture of an LCD constituent element such as a liquid crystal polarizing plate or a phase difference plate; the manufacture of a PDP constituent element; and the manufacture of other various display constituent elements; Or a variety of other optical element parts; or the manufacture of ceramic green sheets; or the formation of protective layers and data recording layers of optical recording media. The release sheet is generally formed by laminating a release agent layer or the like on a base material such as a polymer film, and a polyphthalide resin is widely used as the material of the release agent layer, but a release agent layer and a base composed of a polyoxymethylene resin. The material has poor adhesion and is easily peeled off from the substrate. Conventionally, in order to improve the adhesion of the release agent layer to the substrate, as described in Patent Document 1, it is proposed that the release agent is laminated on the substrate, and the bottom of the substrate is carried out by using a stone-like coupling agent. The method of painting. However, according to this method, it is necessary to increase the coating step of the decane coupling agent, which causes a cost increase, and at the same time, there is a problem that a part of the decane coupling agent in the production is evaporated and deposited in a manufacturing apparatus or the like. Further, in Patent Document 2, in order to improve the adhesion, a release agent composition comprising an oxime and an oxime coupling agent is used to form a release layer, and Patent Document 3 discloses a branch. A stripping agent composition of an organopolyusocyanine and an addition reaction type polyoxyxylene resin. A [Patent Document 1] 曰本特开昭64-5838号 200827407

Japanese Patent Publication No. 2003-26925, the disclosure of which is incorporated herein by reference. =:: In the case of the adhesion force of the adhesive, the separation force is increased. ==############################# 'And the adhesion to the substrate of the release agent layer is good and the package is 系 Π Π Τ Τ Τ 反应 反应 反应 = = = = = = = = = = = = = = = = An alkaloid, ί,:' chain and a branched-chain organic aggregating polyoxygen-based composition having an alkenyl group, the lyophilic composition of the composition is relative to The ratio of the number of soils contained in the composition is 〇·〇2~〇·〇8 (mole ratio). In this case, in the above branched organooxane oligomer, the number of alkenyl groups is preferably 莫·2 to 5·5 in terms of the molar ratio of the methyl groups. Further, in the present invention, the sheet is formed on at least the surface of the substrate to form a cured film of the addition reaction type polyoxygen release agent composition. The effect of the present invention is as described above, and the present invention makes the fluorenyl group to methyl group in a stripper composition containing an addition reaction type polyoxonium grease and a branched organosiloxane atomic oligomer. When the ratio of the number is within the range of the setting, a release sheet having excellent peelability and adhesion between the substrate and the release agent can be obtained. 200827407 [Embodiment] The best aspect of the invention according to an embodiment of the present invention is an addition reaction type polyoxazine stripping composition comprising an addition reaction type polyoxo resin, branching The organic cerium oxide oligomer, the crosslinking agent, and the catalyst may be added, and an addition reaction inhibitor, a release modifier, a adhesion enhancer, or the like may be added as needed. also,

In the hardening step after the application of the toughening agent, a photopolymerization initiator may be added when ultraviolet irradiation is performed in addition to heating. ',,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,, At least one of them. Wherein the 'alkenyl group can be, for example, B: in some way; there is a 'heart' = less

RaR(3-a)Si〇(R2Sj〇)nSfR^^

(I), wherein R is a monovalent hydrocarbon group of the same species, Rl A : the same species of the sacrosin bond; and Kb < 3, /, ,, earth. Further, 100 〇 SiiS500 〇 (1) Further, the hydrocarbon group is preferably a hydrocarbon group, and for example, one of 2 (ex most preferably a carbon number of 1 to 10) is sold in 200827407, for example, a carbon number of 2 to 10 such as an ethylene group, a propyl group or an acryl group. Silk reduction, 癸 癸 ^ ^ 述 有 有 有 有 有 有 有 有 有 有 有 有 有 有 有 有 有 有 有 有 有 有 有 有 有 有 有 有 有 有 有 有 有 有 有 有 有 有 有 有 有 有 有 有 有/〇 is a methyl group. Oxane LlX!7丨Polyorganosteroid having at least 2 alkenyl groups as a functional group, 'Polydimethylene as a functional group with a vinyl group as a functional group As the oxirane oligomer, a siloxane oligomer having a side chain of a fluorene skeleton having a side chain from a main chain oligopolymer can be used. Branched organic oxirane ^ 3 / Ϊ The side chain of the money-burning skeleton is formed by branching more than one branch from the main chain, and at least one of the side chains has a gynecological group. The _ looking oligomer can also be: having a side containing the celestial oxygen Chain star a polymer, or any one of two or more fluorene-type oligomers containing a side chain of a celestane a frame. A knife-like organic compound; an oxygen polymer such as 'the following formula (9) ·

In the formula, R4 represents a monovalent hydrocarbon group, and at least two of all R4 are alkenyl groups such as vinyl, and wherein R4 represents a monovalent hydrocarbon group, preferably 8 〇mol/〇 is a fluorenyl group. Further, 1 $ t $15, while 卩~^^" is such that the number average molecular weight (Mn) of the branched organooxane oligomer is in the range of 5 Å to 5,000. In the alkane oligo, the number of alkenyl groups is preferably from 0.2 to 0.5 with respect to the number of methyl groups. The molar ratio is from the branched organic oxime.

The oxyalkylene oligomer was obtained by analyzing the spectral absorption peak area obtained by 1 H-NMR analysis. The knife-shaped organooxane copolymer is added in the release agent composition in such a manner that the molar ratio of the alkenyl group to the methyl group is ~〇(10). The molar ratio is obtained from the peak of the spectrum obtained by precipitation of the release agent composition by 1H_NMR*. When the molar ratio is less than (10) 2, the film strength is insufficient, the release agent may easily fall off from the substrate, and if the molar ratio exceeds G.G8, the coating film formed by the release agent composition is applied. The joint density becomes high, the peeling force becomes large, and the peeling performance is deteriorated. Further, although the above-mentioned addition reaction type polyoxane can form a film having a relatively high average peeling force, if it is used alone, the film strength is insufficient, and the adhesion to the substrate is poor. In the present embodiment, the number of the added alkenyl groups is in a specific ratio and the number is flat, and the lower of the above-mentioned branched-like oxy-oligomer oligomers can be stripped, for example, having at least 2 bonds in the molecule. = 子 虱 虱 虱 有机 有机 有机 有机 虱 原子 原子 原子 , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , ,于1丝200827407 A polymer, with a trimethylphosphonyl group blocking the terminal poly(methylhydroquinone oxygen =), poly(hydroquinone sesquioxane), etc. In this embodiment, by means of The addition reaction of the agent =SiH' with the addition reaction type polyoxynoxy resin and the alkenyl group of the branched organic oxyalkylene terpolymer forms a hardened film. The crosslinking agent is used to bond the release agent composition to The molar ratio of the number of hydrogen atoms of the halogen atom to the number of alkenyl groups is 0. 8 to 5.0, preferably. The molar ratio is a spectral absorption peak obtained by 1H-NMR analysis of the stripper composition. When the above molar ratio is 〇.8 to _, the hardenability of the composition is lowered, and if it is greater than 5.00, the stripping agent is peeled off. When the concentration is large, the peeling performance may be deteriorated. For the catalyst, for example, a platinum-based compound, a platinum-based compound such as fine-particle platinum, fine-particle platinum adsorbed on a carbon powder carrier, chloroplatinic acid, or alcohol-modified platinum may be used. A three-catalyst such as an acid, a chloroplatinic acid olefin, a palladium or a rhodium catalyst, and a platinum-based metal, which is equivalent to about 1 to a total of an addition reaction type polyoxo resin and a crosslinking agent. Adding 1 〇〇〇 ppm. The release agent composition of the present embodiment is added to, for example, an organic/trol agent, and the solution of the release agent composition is applied to a substrate composed of a polymer film or the like. Thereafter, the film is cured, whereby a cured film having the above-described composition formed on one surface of the substrate as a release agent layer can be obtained. The above-mentioned hardening can be performed by heat hardening, except for heat removal in the hardening step. Ultraviolet irradiation may be performed. For the release sheet, the adhesive layer and the substrate on the side of the adhesive layer may be sequentially disposed on the release agent layer to form an adhesive body. Further, in the present specification, the number is averaged. Molecular weight (Μη) Each of the polyfluorene oxide resins was measured by gel permeation chromatography (GPC) using tetrahydrofuran as a developing solvent, and the results were determined by the difference of the values. The measurement conditions are as follows. GPC measuring device: HLC-8020 (trade name, manufactured by Tosoh Corporation) GPC pipe inspection (hereafter passed): tsk guard column HXL_H, TSK gel GMhxl (χ2), TSK gel G2000HXL (all of the above are trade names, Tosoh Company system)

The solvent was measured: tetrahydrofuran, and the measurement temperature was 40 ° C. Further, 1H-NMR was analyzed under the following conditions.

Measuring machine · AVENCE500 (product name, BRUKER BIOSPIN company), 5〇〇mHz

Measurement solvent: heavy gas imitation, measurement temperature: 23 t: [Examples] The present embodiment is described using the following examples, but the present invention is not limited to the constitution of the following examples. [Example 1] 100 parts by mass of an addition reaction type polyxanthene resin solution (trade name: KS-3656A, manufactured by Shin-Etsu Chemical Co., Ltd., containing polyorganohydroquinone as a crosslinking agent) in a solid content of 30% by mass (30 parts by mass of the solid content), a branched organosiloxane oligopolymer having a solid content of 100% by mass (trade name: X62-1387, manufactured by Shin-Etsu Chemical Co., Ltd., containing polyorganohydroquinone) 10 parts by mass of the crosslinking agent was diluted with a toluene solvent to a solid concentration of U) by mass%. To the diluted solution, a platinum-based catalyst (trade name: PL-50T, manufactured by Shin-Etsu Chemical Co., Ltd.) was added in a ratio of 1 part by mass to obtain a solution of the release agent composition. The solution of the release agent composition was applied to a PET film substrate (trade name: Τ-100, manufactured by Mitsubishi Polyester Co., Ltd.) having a thickness of 38 μm so that the film thickness after drying was 〇·1 μm, and then 150 Drying at ° C for 30 seconds 'obtained a release sheet having a release agent layer laminated on the substrate. Furthermore, the combination of KS-3656A, X62-1387 and stripper respectively

11 200827407 The material was subjected to ^-NMR analysis, and the intensity of the absorption peak of the spectrum was determined to obtain the molar ratio as follows. That is, in KS-3656A, the molar ratio of the number of alkenyl groups to the number of methyl groups is 〇·〇19. In X62-1387, the molar ratio of the number of alkenyl groups to the number of methyl groups is 0.31. In the stripper composition (except for the solvent), the ratio of the number of rare bases to the number of oxime groups was 0.045 (mole ratio), and the molar ratio of the number of hydrogen atoms bonded to the ruthenium atom to the number of alkenyl groups was 1.8. Further, in the present embodiment, the alkenyl group is a vinyl group. Then, the number average molecular weights (?n) of KS-3656A and X62-1387 were measured, which were 197,000 and 1〇90, respectively.

[Example 2] A release sheet was obtained in the same manner as in Example 1 except that the film thickness after drying of the release agent layer was changed to 1 μm. [Example 3] In addition to Χ62-1387 (branched organodecane oligo) relative to KS_3656A (forced reaction type polyoxyxyl resin solution) 1 part by mass (solid content: 30 parts by mass) A release sheet was obtained in the same manner as in Example 1 except that the amount of addition was changed to 5 parts by mass. At this time, in the ruthenium-NMR analysis of the release agent = compound, in the release agent composition (except for the solvent), the molar ratio of the number of alkenyl groups to the number of methyl groups is G, and is bonded to the stone atom The molar ratio of the number of hydrogen atoms is i 8 . [Example 4] Except that X62-1387 (branched organic oxygen = 6 bis reaction type polychelate II) phase phase: 2 = η, the amount of addition was changed to 20 parts by mass, and peeling was performed according to two t Sheet. (4), for the stripping agent, except = she is, the solvent is bonded to the (four) sub-domain material. 12 200827407 [Comparative Example 1]

[Comparative Example 2] In addition, Χ62-1387 (branched organooxyl olefin oligomer) was added in an amount of 30 parts by mass relative to KS-3656A (addition reaction type polyoxyxylene resin solution). The addition amount was changed to 3 parts by mass, and the (four) sheet was obtained in accordance with the method of Example 1. At this time, in the iH-NMR analysis of the bismuth agent composition, in the release agent composition (except for the ☆ agent), the molar ratio of the alkenyl group to the fluorenyl group is 010, and the hydrogen atom of the ruthenium atom The molar ratio of the number of atoms to the number of alkenyl groups is 18. (1) Initial peel force

= _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ A release sheet was obtained in the same manner as in Example 1 except for the mass portion. At this time: in the analysis of the release agent composition, in the stripper composition (except 1 solvent), the molar ratio of the alkenyl number to the fluorenyl group is read 7, bond, σ, σ; The molar ratio to the alkenyl number is ip. An acrylic adhesive (trade name: BPS-5127, manufactured by Toyo Ink Co., Ltd.) was applied on the surface of the release agent layer film of each of the release sheets at a coating amount of 24 g/m2 to form an adhesive layer. Then, PET (product name: "such as ^ E20 #50, manufactured by Toray Industries, Inc.") having a thickness of 5 μm of the adhesive layer side substrate was superposed on the adhesive layer, and then rolled back and forth once with a roller. The adhesive was applied to obtain an adhesive. The adhesive was placed at a temperature of 23. (:, humidity of 50% for 1 day. Then, the adhesive was cut into a width of 20 mm, and the temperature was 23 ° C, and the humidity was 50%. Under the conditions, a Wanyue tensile tester (trade name: TENSILON UTM-4-100, manufactured by Odentech Co., Ltd.) was used, and the substrate on the side of the adhesive layer was placed along the side of 18 〇. The peeling force at this time was measured at a speed of 〇mm/min, and the peeling force at this time was measured. Further, 'the peeling force was 50 mN/20 mm or less as good peeling force' and it was marked as 〇 in Table 1; the peeling force exceeded 50 mN/20 mm. The peeling force is too large, and is marked as X in Table 1. Field (2) Pendulum type wear (study) After the peeling force increase rate y, the peeled sheet is stored at a temperature of 40 ° C and a humidity of 80%. After that, it was ground using a friction fast tester (trade name: RT-2〇〇, manufactured by Seiki Co., Ltd.). Specifically, it will be used as a research/PP80 film ( Product name: Ar〇maAE_u 'made by Showa Denko Co., Ltd.), grinding the side of the release agent layer back and forth 10 times under the weight of 200g, such as the first m ^, and setting the linear grinding in the central part of the peeling sheet 1〇; Adjacent to the side of the release agent layer side, the width 2 of the surface of the driller sheet 20 is placed on the release sheet 1 ,, and it is bonded by a 2 kg roll for 10 times to obtain an adhesive body 30. At this time, For example, the adhesive sheet 20 is perpendicular to the grinding portion of the product in the longitudinal direction: Ϊ Ϊ NO Π Π Π Π Π Π Π Π Π Π 丙烯酸 丙烯酸 丙烯酸 丙烯酸 丙烯酸 丙烯酸 丙烯酸 丙烯酸 丙烯酸 丙烯酸 丙烯酸 丙烯酸 丙烯酸 丙烯酸 丙烯酸 丙烯酸 丙烯酸 丙烯酸 丙烯酸 丙烯酸 丙烯酸 丙烯酸 丙烯酸 丙烯酸 丙烯酸 丙烯酸 丙烯酸 丙烯酸 丙烯酸 丙烯酸 丙烯酸 丙烯酸 丙烯酸Place at room temperature of 23 C and humidity of 50% for 3 minutes. Then use the universal tensile tester described above to pull the substrate of the adhesive sheet 2 at & = to ' at 5 〇 m/min. Then, it is separated from the peeling sheet i. Then, the peeling force ρι of the polished portion W1 and the non-grinding force P:' are measured, and P1/P2 is expressed by %, and the rate of increase of the peeling force after the pendulum type wear is set. After the abrasion loss is 100 to 15 G%, the change in peeling force caused by friction is recorded as follows. The outsider is referred to as the peeling force, and the second is recorded as X. Muyi i < 5 ) 14 200827407 (3) Curing property confirmation test The peeling agent layer of the peeling sheet was rubbed 10 times with a finger, and the film was judged for the presence or absence of the film by rubbing ( Smear) takes place. In the table, the hardening property is determined by visual observation _, X is the viscosity of the paste, and the hardening property is not ^: the wiping (terminating (4) adhesion confirmation test, the peeling agent layer of the peeling sheet is rubbed with a finger, and the film is observed. It is rubbed off (10) 呦. In the watch, it is not rubbed = the adhesion is good), and X is the rub off (determination of poor adhesion). [Table 1] Initial peeling force Pendulum type wear-off peeling force increase rate [%] Determination of wipe rub f [mN/20mm] Judgment ~ Example 1 40 〇 135 〇〇 Example 2 32 〇130 〇〇KJ 〇Example 3 35 〇 125 〇〇〇 Example 4 42 〇 135 〇〇〇 Comparative Example 1 28 〇 250 XXX Comparative Example 2 100 X 110 〇〇〇 From the results of Table 1, it is apparent that the number of alkenyl groups in the stripper composition is 曱 曱In Examples 1 to 4 in which the ratio was in the range of 0.02 to 0.08, the peeling force was good, and the adhesion of the release agent layer to the substrate was good. Further, it is understood that even if the friction release agent layer is used, the peeling force and the hardenability of the release sheet are small, and the physical property stability to friction is high. On the other hand, as shown in Comparative Example 1, when the ratio of the number of alkenyl groups to the number of methyl groups is less than 0.02, the adhesion of the release agent layer to the substrate is low, and the physical property stability against friction is low, and the desired peeling cannot be obtained. Sheet. Further, as shown in Comparative Example 2, it is understood that when the ratio of the number of alkenyl groups to the number of methyl groups is larger than 〇·08 ', the initial peeling force becomes too large, and the peeling property is deteriorated. \ 5 ? 15 200827407 [Simple description of the diagram] The first figure shows the pattern used to determine the rate of increase of the peeling force after the pendulum type wear. [Main component symbol description] ίο peeling sheet 20 adhesive sheet 30 adhesive body W1 abrasive portion W2 non-abrasive portion

16

Claims (1)

200827407 X. Patent application scope 1· 2· Formation reaction type poly-type stripping reaction type polyoxynoxy resin, and initial _, l 3 addition chain, or in its side chain and main chain Hi organic oxy-xanthene skeleton a side oligomer; a chain branched alkenyl branched organooxane composition> characterized in that the molar ratio is G.G2~0.f8, the number of methyl groups contained in the composition = In the addition reaction type-concentration described in Item 1 of the first step, the above-mentioned branched form has a molar basis (4) base number relative to the base number of the (4) base. The hardened film of the addition reaction type polyoxoquinone stripper composition of the above-mentioned patent item 帛1 or 2 is formed from the sheet/characterized at least on the surface of the substrate. 3.