TW593547B - Solvent type silicone composition for mold release agent - Google Patents

Abstract

To obtain a solvent type silicone composition for mold release agent having a curing rate higher than that of the conventional one, providing a cured coating film with a light peel at a high-speed peel, having a slight change in peel force with time of cured coating film, a readily adjustable peel force, being readily handled and even in the case of using a substrate with low heat resistance such as a plastic film as a substrate for a release paper, exhibiting an excellent adhesion to the substrate. This solvent type silicone composition for mold release agent comprises (A) a branched organopolysiloxane which contains two or more alkenyl groups in one molecule and has a structure represented by the general formula: M1aTbDcM2d, (B) an organohydrogenpolysiloxane containing three or more hydrogen atoms bonded to silicon atoms in one molecule, (C) a catalytic amount of a platinum-based catalyst, (D) an addition reaction inhibitor and (E) an organic solvent.

Description

593547 A7 B7 V. Description of the invention (i. After the present invention is related to the surface, a non-polysilicone composition can be formed. In the prior art, the adhesion between substances or the solidification of the silicon oxide composition hardens the substrate and the hardened film is based on the base compound. Catalyst, method for attaching polysulphonium oxide, (2) demoulding with hardened coatings such as paper, laminated plastic paper, plastic film, etc. after condensation reaction using hydroxyl group or alkane for condensation reaction The solvent type of the agent is used as an anti-adhesive material on the surface of the membrane, so as to contain a reaction organotinyl group on the paper, and a method of peeling off the aliphatic alkenyl group, and then on the surface of the compound organic polymer material. Thin plastics are generally used for sex. Known organic substrates and other organic substrates, such as organic silicon oxide, form a peeling film, and other substrates are shaped as ... Adhesiveness is formed to form a polysilicone group. 1) Using a salt catalyst of a platinum system and an organic hydrogen ionizable film, a method of hydrogenating a polysilicon film, etc. (Please read the precautions on the back before filling this page). Ministry of Economic Affairs Bureau employees consumer cooperatives printed (where

r r3 ^ 1 ^ R1, 0--S 〇- a 丨 丨 丨 _ — -S i — 〇- [&J; k 2 R2 —Si-R as the peeling required for this kind of polysiloxane coating In addition to the peeling characteristics of low-speed peeling, recently, it is more required to have high-speed rewinding. In order to remove label residues at high speeds, a polysilicone film attachment method that has easy peeling characteristics at high-speed peeling can be used. ) A method of forming a peelable film after an additional reaction between an aliphatic alkenyl-based organic polysiloxane and an organic hydrogenated polysiloxane. In this case, as an example of the aliphatic alkenyl-containing organopolysiloxane, a linear organopolysiloxane represented by the following general formula (Chem. 6) can be used. 〔Chemical formula 3〕 R2 (6) R1 is aliphatic alkenyl, R2 is substituted or non-substituted 1 valence ~ Table paper size applies Chinese National Standard (CNS) A4 specification (2 丨 0, 乂 297)- 4-593547 A7 ___B7 V. Description of the invention (2) Organic group, R 3 is a substituted or unsubstituted monovalent saturated organic group, e is 2,000 to 20,000, and f is 2 to 2,000. ) (Please read the precautions on the back before filling in this page) However, when using linear organic polysiloxane, low-speed and high-speed peeling and easy peeling characteristics cannot be obtained. Therefore, it has been revealed that high-speed easy peeling and improved hardening For the purpose of using the fat-containing organic polysand oxalate composition with a branched structure containing RS 〇3 / 2 units, JP-A No. 63 — 251465, JP No. 3 — 019267, and JP No. 9 — 0 78032, Japanese Patent Application Laid-Open No. 1 1 — 193366. However, the branched structure lipid-containing organopolysiloxanes not mentioned in these publications can be used to obtain release paper that is easy to peel under high speed peeling, but it is not easy to obtain easy to peel under low speed peeling. Peeling release paper. Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs. Recently, plastic films used as the substrate for release paper have stable quality, high smoothness, easy film formation, and easy access to various varieties. Therefore, the amount of use has increased. When using a plastic film as a base material for release paper, the problem lies in the lack of adhesion between the base film and the polysiloxane film. The plastic film originally had low heat resistance. It tends to be more accelerated). Therefore, it is not possible to increase the curing temperature of the polysiloxane stripper composition. Each of these publications also describes that a composition using an organopolysiloxane containing a branched aliphatic alkenyl group exhibits good hardenability. However, it is currently required to improve hardenability at lower temperatures. In view of the adhesion between the base film and the polysiloxane coating, it is disclosed in No. 3-0 1 9 2 6 7 that the use of a composition containing a branched structure of an aliphatic alkenyl-containing organic polysiloxane has enhanced hardenability. Effect 'However, at lower curing temperatures, good adhesion cannot be obtained sufficiently. As mentioned above, it is required to obtain hardening, high speed peeling, and easy peeling hardness: this paper size applies the Chinese National Standard (CNS) A4 specification (210X297 mm) 593547 A7 __ B7_ _ V. Description of the invention (3) The film is a solvent-based silicone composition for a release agent that is a low-heat-resistance base material such as a plastic film used as a base material for release paper. The object of the present invention is to provide a hardened film with good hardening property, which is easy to peel off under high-speed peeling, and shows a low-heat-resistance base material such as a plastic film as a base material for release paper. Solvent type polysiloxane composition for release agent with good adhesion. [Method for Solving the Problem] A solvent-based polysiloxane composition for a release agent composed of the following (A), (B), (C), (D), and (E) m. (A) A branched organopolysiloxane having two or more aliphatic alkenyl groups in one molecule, having a structure represented by the following general formula (1), and having a viscosity of 5 0 0 P a · s or more at 25 ° C [Chemical formula 4] Μ 1 a T b D c Μ 2 d ... (1) [In the formula, M1 represents the general formula (2), D is the general formula (3), and D is the general formula (4) And M2 represent the structural unit shown in the general formula (5). In the formula, after the oxygen atom shares with the adjacent structural unit, a polysilicon oxygen bond # is formed. R 1 is an aliphatic alkenyl group, R 2 is a substituted or unsubstituted monovalent organic group, a is 2 or more, b is an integer of 5 to 100, c is an integer of 2,000 to 20,000, and d is 0 or positive An integer that satisfies the number of b + 2. ] [Chemical 5] gg This paper size applies Chinese National Standard (CNS) Α4 specification (210 × 297 mm) (Please read the precautions on the back before filling this page) • P Pack '

Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs of the 1T-6-593547 A7 B7 V. Description of the invention (〇 2 R 1 ~ Si-0-R2 (2) 〇 • 〇 —s'i-O- (3) R2 • 〇 —S 丨 一 〇- (4) (Please read the notes on the back before filling this page) R2 (5) R2 — S 丨 i 〇 一 (B) 1 molecule has more than 3 bonds to silicon The atomic hydrogen atom's molar number of hydrogen atoms bonded to the silicon atom is equivalent to 1 to 5 times the molar amount of the total molar number of aliphatic alkenyl groups in (A), and (C) is a platinum-based catalyst in the catalyst amount. (D) Additional reaction inhibitor 0. 〇1 ～ 10 ％ by weight, (E) organic solvent printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs 100,000 ～ 10,000 ％ by weight. Aspect] Hereinafter, the present invention will be described in detail. The branched organic polysiloxane having two or more aliphatic alkenyl groups in one molecule of the component (A) in the composition of the present invention is represented by the general formula (Chem. 1) Structure: In the formula, R 1 is aliphatic alkenyl group such as vinyl, allyl, and propenyl, and R 2 is fluorenyl, ethyl, and propyl yy / This paper is applicable to China National Standard (CNS) A4 regulations Lattice (210 > < 297 mm) -7- 593547 A 7 _ B7 V. Description of the invention (5) Alkyl groups such as butyl; cycloalkyl groups such as cyclohexyl; lipids such as vinyl, allyl, and propenyl Alkenyl; aryl groups such as phenyl-tolyl, or chloromethyl, trifluoropropyl, cyanoethyl, etc. substituted by halogen atoms, cyano, amine, etc., for the hydrogen atoms that part or all of these groups are bonded to carbon atoms Equivalently substituted or unsubstituted monovalent hydrocarbon groups, more selected from alkoxy groups such as methoxy, ethoxy, propoxy, and methoxyethoxy, hydroxyl, epoxy, and the like Those with a monovalent organic group. R 1 is a vinyl group which is more suitable for industrial use, and R 2 contained in the branched organopolysiloxane of component (A), at least 80 mole% of which is methyl, is industrially (A) The branched organopolysiloxane based component has two or more aliphatic alkenyl groups in one molecule, but if it is less than two, it may remain uncrosslinked after curing. It is not ideal to reduce the sclerosis of the molecule. Ideally, the aliphatic alkenyl group content of 100 g branched organopolysiloxane is 0.001 mol ~ 0 · 1 mol, and it is preferably less than 0 · 0 0 1 mol reduces the sclerosis. Conversely, greater than 0 · 1 mol, the pot life is too short to use. The general formula (chemical formula 1) b determines the number of branched organic polysiloxane branches. It is usually an integer from 5 to 100. When it is lower than 5, the number of branches will decrease. The effect of lightening the peeling force under high-speed peeling will be insufficient. On the contrary, if it is greater than 1,000, it will be difficult for industrially stable manufacturing. The more preferred is 6 to 8 0. c is 2, 0 0 0 to 2 0, 0 0, lower than 2, 0 ◦ ◦ the workability will be poor, and greater than 2 0, 0 0 0 will not workability good. Ideally, 5,000 to 10,000 ° a, b are the number of siloxane units at the end of the branched organic polysiloxane molecule, generally a is 2 or more, and d is 0 or a positive integer. The branch Q8 paper standards are applicable. National National Standard (CNS) A4 specifications (210X 297 mm) (Please read the precautions on the back before filling this page) Order printed by the Intellectual Property Bureau of the Ministry of Economic Affairs Consumer Cooperatives -8 -593547 A7 ___B7 V. Description of the invention (6) (Please read the notes on the back before filling out this page} The relationship between the number and the number of molecular ends depends on the number of a + b + b + 2. The aliphatic alkenyl group must have The structural unit is M 1, and a is 2 or more, which means that the number of aliphatic alkenyl groups in the molecule is 2 or more, which means that the aliphatic alkenyl group is preferentially arranged at the end of the molecular chain. When d = 〇, as long as a + If d = b + 2, d = 〇 is more desirable to achieve good hardenability. When a + b is less than b + 2, the physical properties of the organopolysiloxane will be unstable, and even cause poor solubility in solvents. It is not ideal if it is gelatinous. The total content of a, b, c, and d is limited to the degree of polymerization of branched organic polysiloxane. Range, and, in fact, it ’s more useful to express in terms of viscosity. The viscosity of highly polymerized polymers is usually represented by the limiting viscosity of 7? I ·, and the limiting viscosity of branched organic polysiloxanes is 7? R. 1 · 〇 ~ 3 · 0 is particularly ideal, when 7? R is less than 1.0, the workability will be poor, and greater than 3 · 0 will reduce the workability. Intellectual Property Bureau of the Ministry of Economic Affairs, the consumer consumer cooperative printed (A) component The synthetic method of branched organic polysand oxygen is that hydrolyzation of trimethoxysilane and aliphatic alkenylsiloxane represented by the following general formula (7) is performed under acidic conditions, and after condensation reaction, it is reacted with octylcyclotetracycline. Siloxane is obtained after polymerization in the presence of an alkali catalyst. Among them, R1 and R2 are the same as the above. [Chem. 6] R2 R2.;

Ri-S: iQ-S'i-Ri ... f, R2 ^ --... (7) The organic hydrogenated polysiloxane of the component (B) in the present invention must have more than 3 bonded silicon in one molecule Except for the atom of hydrogen, there is no special limitation on the size of miscellaneous paper. The Chinese National Standard (CNS) A4 specification (210X297 mm) 593547 A7 B7 is used. 5. Description of the invention (7). The molecular structure can be as long as 5 m P a

Ming Jiafa T This example is shown in Formula 7 as Formula 1. The specific component of (B) in C f linear, branched, or cyclic • s ~ 100 mPa. The present invention is not limited to this. Any of them. In addition, the viscosity should be within the range of 'S. For example, the following statement has been written (Chemical 〇 e 6 MISIM I e rMi rM e ^ rH e ^ I-one S i 〇 I 1 one S [0 I I L H J 1 LM e J Si rU e Λ rU e Λ e

M —SIM I H e 6 — · S i OI iV-M e

—S i O I H ^ rM e λ j e ^ one S i Οι — | S i 0_ I Ih ”k 1 LMe J

Me S i —Η j Me ------------- C Please read the notes on the back ¾ before filling out this page) Order Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs

M —SIM i e M 6 e h Ji j 1 three mouths, the next is ί γ rUe Λ rMe,

M e-one S 〖〇 ---- S i 0 -S i 0I V, X ^ π λ; Γ e H ΓΓ Me ee M 丨 SIM IH ru e) fiVi e) rUe Λ 1 -S i O 1 one S i〇I 1-S i〇I l H ^ q 1, Me ^ r 1 L y JM e I s Μ Η% e § In each formula, Μ e is methyl and χ is γ. General formula (9) The basic test of the show, Qiao (8 "CNS) A4 size (210X2 ^^ 7

-1CU 593547 A7 B7 V. Description of the invention (5) 0, 0, 1, PS is 1 to 5 0 0, h Λ i, r, t, u V 'w is the number of r 0 to 5 0 0. rM e λ rU e Me:-〇- 1 -S i I 〇—- 1 —Si 〇— 1 -S i-| -Me '. (8) 1 LHJ 1 e J u Me e 「Me " Λ Me Y = —O · 1. "Si 〇1 1 — Si 〇__ 1 -S '丨--H. (9) 1 LHJV 1 kM e J w Me (Please read the notes on the back before filling this page ) In the present invention, the compounding amount of the component (B) of the organohydrogenated polysiloxane is that the hydrogen atom (hereinafter referred to as S i-) of the bonded silicon atom has a mole number equal to the total number of aliphatic alkenyl groups in (A). The amount of 1 to 5 times the number of ears. When the Si-mol number contained in the compounding amount of the (B) component is less than 1 times (A) the total number of aliphatic alkenyl moles, the hardenability is insufficient, and vice versa If it is more than 5 times, there is no obvious effect, but it causes the degradation of the peeling performance over time, and the economic aspect is not ideal. From the above records, the organic hydrogenated polysiloxane of the (B) component is targeted at the (A) component of 100%. The blending amount in parts by weight is from 0 · 1 to 20 parts by weight. The consumer cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs prints the platinum group catalyst promoter (A) component and (B) component of the component (C) in the present invention. Attach Reaction, used to form a hardened film. Take platinum group catalysts as examples, such as platinum black, platinum chloride, platinum chloride-olefin complex, lead chloride-alcohol complex, germanium, Examples of germanium-olefin composites. The amount of (C) component is based on the total amount of (a) component and (B) component as platinum amount or money amount. 5 ~ 1, 000ppm is easier to form good hardening. The filmed person can respond to the QA of the two components (A) and (: B). The paper size is applicable to the Chinese National Standard (CNS) A4 specification (210X297 mm). -11-Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs 593547 A7 ___B7_ V. Description of the invention (9) The reactivity or the desired curing rate is appropriately increased or decreased. The additional reaction inhibitor of the (D) component in the present invention can be known. For example: 3-methyl-1 monobutyl Acetylene alcohols such as alkyne-3, alcohol, 3,5-dimethyl-1-hexyne-1, 3-methyl alcohol, 3-methyl-1, 1-pentene-3 alcohol, phenyl butanol; 3-methyl —3 -pentene—1-acetylene, 3,5-dimethyl-1,1-hexyne—3-acetylene and other vinyl compounds; such acetylenes Reactants of compounds with alkoxysilanes or alkoxysiloxanes or hydridosilane or with hydridosilane; ethylenesiloxanes such as tetramethylvinylsiloxane rings; organic nitrogen such as benzotriazole Compounds and other organic hydrazone compounds; examples of oxime compounds, organic chromium compounds, and the like. (D) The compounding amount of the component is only about 12 hours at the room temperature, and the stability of the treatment bath can be obtained. It is 0.01% by weight of the component (A) It is preferably from 10 to 10 parts by weight, and more preferably from 0.1 to 1 part by weight. The organic solvent of the component (E) in the present invention is for the purpose of improving the storage stability of the processing bath and the coating properties of the composition of various substrates, adjusting the coating amount and the viscosity of the bath. For example: toluene, xylene, ethyl acetate, acetone, methyl ethyl ketone, hexane, etc. can be uniformly dissolved in the composition of the present invention, and an organic solvent that does not react with the cross-linking agent and the inhibitor can be used. The composition of the present invention can be easily manufactured by uniformly mixing (A), (B), (C), (D) in (E). When performing this mixing, first, the component (A) is uniformly dissolved in the component (E), and then the components (B) and (D) are preferably mixed. In order to ensure a sufficient pot life, the (C) component is added to other components before the low peeling is added. The paper size of this invention applies to Chinese National Standard (CNS) A4 specification (210X297 mm1 (Please read the precautions on the back before filling in this page)

-12- 593547 A7 ______B7 V. Description of the invention (10) When necessary, the composition can also be mixed with inorganic fillers or pigments such as sand dioxide. (Please read the precautions on the back before filling in this page.) When using the composition of the present invention to make release paper, etc., dilute the composition of the present invention directly or as appropriate with an organic solvent, and then apply it with a rod coating or roller coating. Layer, reverse roll coating, photocopying coating, air-scraping coating, and more in the film coating process, using a variety of well-known coating methods such as high-precision compensation tank coating, multi-stage roll coating, etc. Coating of substrate. The coating amount of the composition substrate of the present invention varies depending on the type of the material of the substrate to be coated. Generally, as a solid amount, a coating amount of 0 · 1 ~ 2. As ideal. In this way, after heating the substrate coated with the composition of the present invention at 80 to 130 ° C for 5 to 30 seconds, a hardened film is formed on the surface of the substrate, and the desired peeling force and residual adhesion can be obtained. Force and other characteristics of the release paper. [Examples] Hereinafter, the present invention will be specifically described by way of examples. However, the present invention is not limited to the following examples. Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs (Modulation of Branched Organic Polysiloxane) -13- 593547 A7 _B7 V. Invention Description (M) (Please read the precautions on the back before filling this page), 5 0 g of 35% hydrochloric acid was added to the dropping funnel, and the temperature was maintained at 0 ~ 5 ° C. The reaction was performed after dropping while stirring. Heat at 0 ~ 5 ° C for 2 hours. After standing, remove the separated acidic water layer, add 100 g of water, stir for 30 minutes, and then let it stand. Repeat the water washing operation to remove the water layer separation. Until the water layer is neutral. After distilling the siloxane layer under a reduced pressure of 2,00 〇 Pa, the unreacted substances and solvents were removed to obtain 300 g of polysand oxygen institute with a viscosity of 20 mm2 / s. After confirming the composition of this polysiloxane by 2 9 S i-NMR, R1 of the general formula (2) is a vinyl group, R2 is a siloxane unit equivalent to 1 mol of methyl group, and R2 of the general formula (3) It is a siloxane which is equivalent to 1 mole of a methylsiloxane unit. 2) The raw material siloxane b (hereinafter abbreviated as M T) is printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs. In addition to using the general formula (7), R1 is methyl, and R2 is also equivalent to methyl hexamethyldiamine. Siloxane 162g (1 mole, hereinafter abbreviated as M2) was used instead of tetramethyldivinyldisilazane, which is the raw material siloxane a, and was prepared in the same way as the raw material siloxane a to obtain a viscosity of 280 g. 2 5mm2 / s of polysiloxane. After determining the composition of this polysiloxane by 2 9 S i-NMR, R2 of general formula (5) is equivalent to 1 mol of siloxane unit of methyl and R 2 of formula (• 3) is equivalent to A silicone hospital made of 1 mole of methyl siloxane. 3) Modulation of branched organic polysiloxane. The paper size is in accordance with Chinese National Standard (CNS) A4 specification (210X 297 mm) -14- 593547 A7 B7 V. Description of the invention (12) (Please read the note on the back first Please fill in this page again) After using octylmethylcyclotetrasiloxane, tetramethyltetravinylcyclotetrasiloxane, VMT, MT, VM2, and M2, the same composition as the expected branched organic polysiloxane After placing the flask into the flask, a 0 · 05 m KM of K〇Η was added to the Si atom placed in the sand oxygen hospital at 1 mole, and the polymerization reaction was performed at 150 ° C for 5 hours, and then at 15 After distillation under reduced pressure of 0 ° C at 0 ° C, unreacted substances and volatiles were removed to obtain branched organopolysiloxane. For this organic polysiloxane, the composition determined by 2 9 S i-N M R is shown in Table 1, a, b, c, and d. The composition ratios shown are branched organic polysiloxanes M 1 a T b D. Μ 2 3 d. (Measurement method of limiting viscosity 7? I •) 1) Determination of absolute viscosity 7? After preparing various concentrations of organic polysiloxane solution (g / 1) in toluene, use a rotary viscometer to measure the absolute viscosity at 25 ° C 7 ?. The absolute viscosity of toluene is 7 ?. Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs. I i) Conversion of specific viscosity Use the above to obtain absolute viscosity / ?, 7 ?. The specific viscosity is calculated by the following formula. Specific viscosity 1 -15- 1 ii) Calculation of limiting viscosity 7? R 2 Plot the specific viscosity of each concentration for concentration (g / 1) to get 3 Straight extrapolate to the limit of concentration 0 g / 1 値 as Limiting viscosity r ° 593547 A7 ____B7__ 5. Description of the invention (13) (Examples and Comparative Examples) (Please read the precautions on the back before filling in this page) [Preparation of polysiloxane composition for release paper] Equipped with a stirring device Inner volume 1 1 Place 30 g of the branched organopolysiloxane as component (A) in the flask, and 5 70 g of toluene as component (E), at 20 ~ 4 0 ° C After stirring to a homogeneous solution, dissolve it. 'Furthermore, if the component (B) is added, the trimethylsilyl group is used to perform pressure measurement at both ends of the molecular chain, and the structural unit shown by 95 mole% M e HS i 2/2 is included, so that the viscosity is When the methyl hydrogenated polysiloxane of 2.5 m P a · s is used for vinyl moles containing (A) component, it contains 1.5 parts by mole of MeHSi 〇2 / 2Kg structural unit by weight, and 1 g of the (D) component 3-methyl-1-butyn-3-ol, was stirred and mixed at 20 to 40 ° C for 1 hour. Before the substrate coating, add the mutual salt of platinum (C) and ethylene siloxane to 50 P P m of the (A) component converted to the amount of platinum, and then adjust the composition. For this composition, each characteristic of Table 2 was evaluated according to the evaluation methods described below. Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs. 1) After adding the hardening catalyst, the surface of the PET film (thickness 40 / m) with a polysilicone composition after 10 minutes is coated with a rod coating to form a solid content of 0.5 g / m2. The amount was heated in a hot-air circulation type dryer at 80 ° C for a predetermined time, and the time until the hardened film was formed was measured. The determination of whether it is completely hardened is based on the paper size formed by manual index friction. The Chinese paper standard (CNS) A4 (210X 297 mm) is applicable. -16- 593547 A7 _______B7 V. Description of the invention (14) Hardened coating The time until there is no fogging or falling off, this time is regarded as hardening. 2) Peeling force: The polysilicone composition after adding the catalyst after 10 minutes is coated on the surface of the PEE film (thickness 40 / zm) with a rod coating to form a solid content of 0.5 g / m. The amount of 2 was heat-treated in a 100 ° C hot-air circulation dryer for 30 seconds, and then a hardened film was formed to form a separator for evaluation. The separator was left to stand at 25 ° C, 50% R, and humidity for 1 day. The liquid-type propylene-based solvent-based adhesive, Olabain BPS, was applied on the surface of the cured film in a wet manner. -5127 (manufactured by Toyo Ink Co., Ltd.), and then heat-treated at 100 ° C for 3 minutes. Then attach a PE ET film (thickness 40 / m) to this treatment surface, press and bond once with a 2 kg roller, and perform edging at 25 ° C for 20 hours, then cut the sample into 50 The width is mm, and the force required to stretch and peel the adhesive tape (N) was measured using a tensile tester at 180 ° angles 0.3 m / min and 60 m / min. This measurement was performed using an automatic graph D C S-500 type manufactured by Shimadzu Corporation. 3) Residual adhesion rate and 2) Peeling force measurement The same method was used for the evaluation of the sub-II device 5 and 10 dagger coating on the surface of the film with poly-adhesive tape, nit-3 1 B tape (trade name made by Nitto Denko Corporation) , Which has a weight of 20g / Cm2 on it, (CNS) Α4ί ^ (210X297 ^^) — —-—- (Please read the precautions on the back before filling this page) Printed by the Intellectual Property Bureau Employee Consumer Cooperatives System-17- 593547 A7 B7 V. Description of the invention (15) 70 ° C, after edging for 20 hours, 'peel off the tape and stick to the stainless steel plate. (Please read the precautions on the back before filling in this page.) Then peel this tape against the surface of the stainless steel plate at an angle of 180 ° '0.3 m / min, and then measure the force required for peeling. A (N). In addition, as a blank tester, the polyester tape was adhered to the surface of the Teflon board, and the edged tape was measured under the same conditions as the force B (N) required to peel off the Teflon board. (A / B) X 1 0 0 is calculated. The residual adhesion rate was evaluated as 95% or more, 90% to 95% as eight, and 90 or less as X. 4) Adhesiveness and 2) Peeling force measurement Using a PET film (thickness 40 // m) made by the same method as the separator of the substrate and an OPP film (4 0 // m, corona treatment) Pass) After replacing the substrate, the separator made by the same method was placed at 25 ° C, 50% R Η (relative humidity), and the surface of the film was hardened by rubbing with fingers, and the surface of the film was turbid and peeled off. . Printed by the Consumers ’Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs 8-„ 5) Variation of the peeling force of the separator over time and 2) The peeling force was measured using a P Ε Τ thin film (thickness 4 0 // m) as the basis After the separator was placed at 25 t, 50% R Η humidity for 1 day, the peeling force was measured in the same manner as in 2). When the peeling force of 2) was measured at 50% or higher, it was recorded as 0, 50. Less than% is X ° (CNS) A4 specification (210X297 mm) -18-593547 A7 B7 V. Description of the invention (16) 6) Application period The solution of the polysiloxane composition for release paper prepared in the examples at room temperature The viscosity increased after standing for 1 day, and it was 〇 below 50 mm 2 / s, and X above 50 mm 2 / s. [Table 1] General formula of the preparation example (1) Viscosity ethylene price No. ab C d V r Mol / 100g 1 2 0 20000 0 3.10 0.01 2 3 3 10000 2 2.93 0.01 3 7 5 10000 0 2.71 0.01 4 10 8 1600 0 0.92 0.01 5 12 10 2000 0 1.34 0.01 6 52 50 10000 0 1.83 0.01 7 102 100 20000 0 2.11 0.01 8 127 125 25000 0 2.48 0.01 9 5 50 10000 47 2.05 0.0007 10 8 50 10000 44 1.97 0.001 11 52 50 10000 0 1.79 0.1 12 0 50 10000 52 1 .83 0.12 13 75 100 10000 27 1.2 0.01 14 75 125 10000 52 0.97 0.01 ί This paper size applies to China National Standard (CNS) A4 size (210X 297 mm) (Please read the precautions on the back before filling this page) Order Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs-19-593547

7 7 AB V. Description of the invention (17 Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs △ F 〇〇〇〇〇〇〇〇〇〇XX 〇〇〇1 〇PP ί 100 100 100 100 ί 1 inch uo 100 ο 100 for 3 PET s S r—H CO 〇S 10 s S 〇〇〇〇〇〇〇〇〇〇〇〇〇〇 〇 Residue residual adherence rate 〇 〇 〇 〇 〇 〇 〇 〇 〇 0 < $ 〇 ι 〇〇〇o inch 0 〇〇 ί—Η 〇〇 bond a 〇VO CO CO inch CN1 CO vo MD CO inch ν〇CNl CNI 0 · 3 m / min 0.20 CO cs o U ~) CO o ir-) r < io Ο ΐ · " < «η cs ο o ^ T) 〇CO C < J o ν / ~ > CO Ο ο ο 1.80 0.65 ID CM soo S ο Ο ο… CO un © CO Ο Γ-Η CO tH < N inch ΟΟ ON OJ inch Ηξ! 11UCL dark r—H inch V j ^ * \ rH y Bu '^ O m Series IK CN CO \ LJ L, V. N vT) χΓ ** /) Parent bond S Regret key (Please read the notes on the back before filling in this page) -Department · 17 Q2Q This paper size is applicable to Chinese National Standard (CNS) A4 specification (210X297 mm) -20- 593547 A7 ____B7 V. Description of the invention (18) [Inventive effect] Solvent-type polysiloxane for release agent of the present invention After the aliphatic polyalkenyl-containing organic polysiloxane used in the composition system is changed from a linear structure to a branched structure, a terminal aliphatic alkenyl group having a higher reactivity than a side chain aliphatic alkenyl group is added, and a higher degree of polymerization After that, high-speed hardening can be performed at low temperatures. After homogenization of the crosslinked density distribution of the hardened film, the adhesion to the substrate can be improved, and after high-speed curing at low temperature, the use of plastics with low heat resistance and difficult to adhere to the substrate can be expanded. In addition, the solvent-based polysiloxane composition for a release agent of the present invention has a hardened film that is easy to peel under high-speed peeling. After the hardened film has passed, the peeling force changes little and is extremely stable. Therefore, it is easy to adjust the peeling force and to use it easily. (Please read the notes on the back before filling out this page) The paper size printed by the Employees' Cooperatives of the Intellectual Property Bureau of the Ministry of Economy applies the Chinese National Standard (CNS) A4 specification (210X 297 mm) -21-Announcement No. 91113298 Patent Amendment page of the Chinese manual of the application Application date 18th of the year Case number Q1112 Grain type year (the above columns are filled in by the Office) January 15, 1993—.Τ1ϊ: ί £ ΐ 593547 Ming Patent Specification Chinese Demolding_new name of invention of solvent-based polysilicon composition

SOLVENT TYPE SILICONE COMPOSITION FOR MOLD RELEASE AGENT Name Nationality (1) Kenji Yamamoto (2) Ishihiko Ogawa (1) Residence and residence of the inventor (4), 1613, Isobe, Annaka, Gunma Prefecture, Japan (2) < Fujitsuka-cho, Takasaki-shi, Gunma Prefecture, Japan-Japanese name (name) (1) Shin-Etsu Chemical Industry Co., Ltd. Shin-Etsu Chemical Co., Ltd.

Printed by the Consumer Property Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs, Nationality III. Applicant's Residence, Residence (Office) Name of Representative (1) Japanese Version (1) Otejiro, Otejiro, Chiyoda-ku, Tokyo, Japan (1) Jinchuan Chihiro paper size is applicable to China National Standard (CNS) A4 specification (2) 0 × 297 mm

Claims (1)

593547 Sixth, the scope of application for patent No. 91113 298 Chinese patent application for amendment of the scope of patent application of the Republic of China on January 5, 1993 Amendment 1. A solvent-based polysiloxane composition for release agents, characterized by the following (A), (B), (C), (D), (E), (A) has one or more alkenyl groups in one molecule, and has the structure shown in the general formula (Chem. 1) below, at 25 ° C The viscosity is 5 0 0 P a · s or more. The limiting viscosity 7? R is 1 · 〇 ~ 3 · 0 in the branched organopolysiloxane is 100 parts by weight '[化 1] Μ 1 a T b D c Μ 2 d ······ (1) [wherein 'M1 represents general formula (2), D is general formula (3), D is general formula (4), and M2 is general formula ( 5) The structural unit shown in the formula, where the oxygen atom and the adjacent structural unit jointly form a siloxane bond, R 1 is a alkynyl group, R 2 is a substituted or unsubstituted monovalent organic group, and a is 2 ~ 1. 2, b is an integer from 5 to 100, c is an integer from 2,00 to 20,00, and d is 0 or a positive integer, which satisfies a + b = b + 2] 〕 This paper music scale applies China National Standard (CNS) Α4 · (2) 〇 > < 297 read) .. (Please read the precautions on the back before filling in the S page) ^ 丨 * 1T Printed by the Employees' Cooperative of Intellectual Property Bureau of the Ministry of Economic Affairs 593547 A8 B8 C8 D8 Patent application scope 〇 2 R 1 — S i — 〇 — R2 (2) 〇〇-S 丨 一 〇 一 (3) R2 〇 一 S. i — 〇R2 R2 R2-S 丨 bu 〇 One k2 (4) (5) (Please read the precautions on the back before filling. Packing-page Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs (B) 1 hydrogen molecule with 3 or more silicon atoms bonded to it For organic hydrogenated polysiloxanes, the mole number of the hydrogen atom of the bonded silicon atom is equivalent to 1 to 5 times the weight part of the total mole number of aliphatic alkenyl groups in (A), and (C) the catalyst amount. The platinum-based catalyst is 5 to 1000 ppm with respect to the (A) + (B) component, 0.01 to 10 parts by weight of (D) an additional reaction control agent, and 100 to 10, 000 as an organic solvent. 0 parts by weight. The size of this paper applies to China National Standard (CNS) A4 (2) 0X 297.mm) -2-