TW200417591A - Silicone adhesive composition and adhesive tape thereof - Google Patents

Abstract

This invention is to provide a silicone adhesive composition and an adhesive tape thereof which can be peeled off without leaving adhesive residue when applied on an object made of metal, particularly stainless steel, to mask them and heated to a temperature as high as 300 DEG C. This invented peroxide curable silicone adhesive composition comprises a diorganopolysiloxane (A), a polyorganosiloxane (B) comprising R<1>3SiO0.5 unit and SiO2 unit in a molar ratio of the R<1>3SiO0.5 unit to the SiO2 unit of from 0.6 to 1.7. Also provided are an addition-reactive silicone adhesive composition comprising a diorganopolysiloxane (A') having 2 or more alkenyl groups, a polyorganosiloxane (B), a hindered amine compound (C) a polyorganosiloxane (E) having SiH group, a retarder (F), and a platinum catalyst (G).

Description

200417591 (1) 发明. Description of the invention [Technical field to which the invention belongs] The present invention relates to attaching an adhesive to stainless steel, etc., and subjecting it to heating and aging at 2800 ° C, but the peeling off of the adhesive does not cause sticky polysiloxane adhesion. Agent composition and adhesive tape. [Prior technology] Adhesive tape using polysiloxane adhesive, the polysiloxane adhesive layer of the adhesive label has good heat resistance, cold resistance, weather resistance, electrical insulation and chemical resistance. Therefore, acrylic adhesives, Rubber-based adhesives, urethane-based adhesives, and epoxy-based adhesives are used under severe conditions of deterioration and deterioration. For example, when manufacturing parts, processing, and heat treatment, be sure to protect the color mask completely or partially and temporarily fix it. This is the ideal silicone adhesive for users who can peel off even after heating at 250 ° C. However, in recent years, it has been necessary to improve the heat resistance of the polysiloxane adhesive compared to the prior heat treatment at a higher temperature. One example is that with the practical implementation of lead non-soldering in the mounting of electronic parts, the reflow temperature of the soldering of electronic parts on the substrate is higher than the previous temperature, and its peak temperature reaches 280 ° C. Therefore, the adhesive cannot be peeled off at this high temperature, and even after the treatment, it must be transferred to the peeler who has no residue on the coating. Adhesive tape using an advanced polysiloxane adhesive is attached to the metal part for color masking. When the adhesive tape is peeled and removed at a temperature of 150-250 ° C -4- (2) (2) 200417591 Adhesive remains on the metal Part, or, from the base material of the adhesive tape, its adhesive layer migrates to the metal part. This is called a residue. This is because the polysiloxane adhesive is degraded by being oxidized after being heated. Along with this, the cohesive force of the adhesive layer is reduced, and the adhesive layer is destroyed. In addition, in the manufacture of semiconductor parts and copper-based lead-frame laminated parts, it is known that after using an adhesive tape containing an antioxidant in a polysiloxane adhesive, even at 200 ° C, the steps do not degrade the adhesive. (Reference Patent Document 1) φ In addition, when a phenol-based antioxidant is contained in the additional reaction-hardening polysiloxane adhesive composition, a polysiloxane adhesive can be obtained without sticking to metals such as copper and attached to metals. It is a cover for copper, copper alloy, iron, etc., and it is color-masked. Even at a high temperature of 150 ~ 250 ° C, there is no residue. It provides a polysiloxane adhesive composition and an adhesive tape that can effectively peel off. (Patent Document 2) However, after the addition of an antioxidant polysiloxane adhesive as described above to give a high temperature of 280 t higher, when the metal, especially copper, copper alloy, iron spring and other metals are removed and stripped, a residue appears. phenomenon. [Summary of the Invention] The object of the present invention is to provide a color mask that can improve the above-mentioned problems by attaching coatings such as metal, especially stainless steel. Even when the high temperature of 280 t is received, no residue will appear and can be effectively peeled off. Silicone adhesive composition and adhesive tape. &gt; [Patent Document 1] -5- (3) 200417591 Japanese Patent Publication No. 3454 15 [Patent Document 2] Japanese Patent Publication No. 200 1-290863 (Japanese Patent Publication No. 2003-96429) For this purpose, after careful discussion, it was found that after adding a hindered amine compound to the polysiloxane adhesive composition, the adhesive was affixed to a metal, especially stainless steel, etc., and subjected to heating and aging at 280 ° C, even if the adhesive was peeled off. The agent still does not baffle stainless steel, which can be effectively peeled off, thereby completing the present invention. As the polysiloxane adhesive composition used in the present invention, for example, an organic peroxide hardening type, an addition reaction hardening type, or the like may be used. Therefore, as the peroxide-curable polysiloxane adhesive composition of the present invention, the following examples can be used. In order to provide polysilicone containing 20 to 80 parts by weight of polydiorganosiloxane (B) containing RSSiOo units and Si02 units, the molar ratio of RSSiOu units / Si〇2 units is 0.6 to 1.7 Oxane (R1 is a monovalent hydrocarbon group having 1 to 10 carbon atoms) 8 to 20 parts by weight (C) A hindered amine compound having a structure represented by the following formula is 100 weight for (A) and (B) in total 0.01 to 1.0 parts by weight

R

R -6-(4) (4) 200417591 (R is a monovalent hydrocarbon group having 1 to 6 carbon atoms) (D) When the organic peroxide hardener is 100 parts by weight in total for (A) and (B). . 丨 ~ 5. 〇 By weight of peroxide-hardened polysiloxane adhesive composition. Further, the present invention provides an adhesive tape in which a hardened layer of the silicone adhesive composition is laminated on at least one side of a rubber film. Examples of the addition reaction hardening type polysiloxane adhesive composition can be used as follows. Provide a polydiorganopolyoxane containing (A ') 2 or more aliphatic alkenyl groups in one molecule. 20 to 80 parts by weight (B) containing RSSiO. ”Units and SiCh units, polyorganosiloxanes with a molar ratio of RSSiOu units / SiCh units of 0.6 to 1.7 (R1 is a monovalent hydrocarbon group with 1 to 10 carbon atoms) 80 to 20 parts by weight (C) Contains the following formula The hindered amine compound of the structure shown is 0.01 to 1.0 parts by weight for a total of 100 parts by weight of (A,) and (B)

R

(R is the same as shown above) (E) The polyorganosiloxane containing SiH group is aimed at the aliphatic alkenyl group in the (A ') component and the SiH group in the (E) component. 7- (5) ( 5) 200417591 The ratio of ear to 0.5 ~ 20. (F) Control agent needle seal (A '), (B) Total s is 0 to 8.0 parts by weight at 100,000 parts by weight (G) The platinum catalyst targets the components (A'), (B) and its total uranium content It is an addition-reactive polysiloxane adhesive composition of 1 to 5000 ppm. In addition, a feature of the present invention is to provide an adhesive tape in which a hardened layer of the polysiloxane adhesive composition is laminated on at least one side of a plastic film. According to the present invention, after coating a metal, especially a stainless steel coating, even after being subjected to a high temperature of 280 ° C, it does not leave a residue, and can effectively obtain a completely peeled polysiloxane adhesive composition and an adhesive tape. [Embodiment] [Best Mode for Carrying Out the Invention] As the peroxide-curable polysiloxane adhesive composition of the present invention, the following can be used. Supplied with. (A) polydiorganosiloxane (B) containing RSSiO. ”Units and SiCh units, RSSiO. Polyorganosiloxanes with a molar ratio of 0.6 to 1.7 units / SiCh units (R1 is a monovalent hydrocarbon group having 1 to 10 carbon atoms) 80 to 20 parts by weight (C) A hindered amine compound containing a structure represented by the following formula 0.01 to 1.0 parts by weight based on 100 parts by weight of (A) and (B) (6) (6) 200417591

R

(R is a monovalent hydrocarbon group having 1 to 6 carbon atoms) (D) The organic peroxide hardener is 0.1 to 5.0 parts by weight of a peroxide-curing polysilicon for a total of 100 parts by weight of (A) and (B) An oxygen adhesive composition. A further feature of the present invention is to provide an adhesive tape in which a hardened layer of the silicone adhesive composition is laminated on at least one side of a plastic film. At this time, these silicone adhesive compositions and adhesive tapes can be effectively used as metal, especially stainless steel color mask tapes. Hereinafter, it will be described in more detail. In the case where the component (A) is polydiorganosaloxanes, the following formula is suitable. RSSiO-(R22SiO) p-SiR23 RS (HO) SiO-(R22SiO) p-SiR22 (OH) where 'R2 is a hydrocarbon group of the same or different carbon number 丨 ~ 10, in order to improve the heat resistance, a sand atom is selected. 0 ~ 35 mole% of all organic groups, especially 2 ~ 20 mole% of phenyl. It is more preferable that the total siloxane unit is from 1 to 35 mole%, and the diphenylsilane unit is particularly from 2 to 20 mole%. p In this polydiorganosilicone plant at 25 ° C, the viscosity is 500 mPa · s or more. Among them, R2 is preferably a valent hydrocarbon group with 1 to 10 carbon atoms, such as: methyl, ethyl -9 · (7) (7) 200417591 Examples of alkyl groups such as alkyl, propyl, butyl, cycloalkyl groups such as cyclohexyl, aryl groups such as phenyl, tolyl, etc. Particularly preferred are methyl and phenyl. . The properties of the polydiorganosiloxane may be oily or rubbery. (A) The viscosity of the component is 25 ° C, as long as it is oily, it is more than 500mPa • s, especially more than 10,000mPa · s. When it is less than 5,000 mPa · s, it is not preferable because the hardenability and the cohesive force (maintaining force) are reduced. In addition, as long as the raw rubber-like substance is dissolved in toluene at a concentration of 30%, the viscosity is preferably 100,000 mPa · s or less. If it exceeds 100 000 mPa · s, the composition is too difficult to stir during manufacture. In addition, the component (A) may be used in combination of two or more kinds. (B) The composition is a polyorganosiloxane containing R ^ SiOo.s units (R1 is a monovalent hydrocarbon group having 1 to 1 carbon atoms) and Si02 units. The molar ratio of the R ^ SiOoj units / Si02 units is 0.6 to 1.7. Alkanes. When the molar ratio of R ^ SiOo.s unit / Si〇2 unit is less than 0.6, the adhesive force is reduced, and when the curl is "1.7", the adhesive force and the retention force are reduced. Examples of R 1 include alkyl, cycloalkyl, phenyl, vinyl, allyl, and hexyl groups such as methyl, ethyl, propyl, and butyl. Also preferred is methyl. (B) The component may also contain an OH group, and the content of the OH group is preferably 4.0% by weight or less. When the OH group exceeds 4.0% by weight, the hardenability of the adhesive is reduced, which is not desirable. In addition, without compromising the characteristics of the present invention, 'may also contain WSiOo.s units, and R ^ SiO units in the (B) component. The component (B) may be used in combination of two or more kinds. The (A) and (B) components can also be used as a simple mixture. When the (A) component contains the following formula, -10-200417591 R22 (HO) Si〇 一 (R22Si〇) p-SiR22 (OH) (p and the above The same.) The components (A) and (B) can also be used as condensation reactants. When the condensation reaction is performed, the mixture of the components (A) and (B) dissolved in a solvent such as toluene using a basic catalyst may be reacted at room temperature to reflux. The proportion of the components (A) and (B) is preferably 20/80 ~ 80/20, especially 30/70 ~ 70/30. When the compounding ratio of the polydiorganosiloxane of the component (A) is less than 20/80, the adhesive force and holding force are reduced. On the other hand, if it exceeds 80/20, the adhesive force and curling property are reduced. (C) The component is a hindered amine compound. In particular, those having the following structure in the molecule are more preferred.

Among them, R is a monovalent hydrocarbon group having 1 to 6 carbon atoms, such as: alkyl groups such as methyl, ethyl, propyl, and butyl, cycloalkyl groups such as cyclohexyl, and aryl groups such as phenyl. For the better. The specific example is as follows. -11. (9) 200417591 CHa C6H5CO.

CH3 CnH23COO

ch3

ch3 OCO ^ CH ^ COO

ch2c〇ox I CHCOOX I CHCOOX CH2C〇〇X

ch2coox I CHCOOX CHCOOX CH2COOX

ch2coox CHCOOX CH〇COOX

12 200417591 (10) ch3 ch3 HaCj &quot; h3c-n ^)-νη · (〇η3) 2 · νη-(N-CH; H3C / 1 W ^ CHa ch3 ch3 (C) (A), (B) 0.01 to 1 part by weight of the component may be sufficient. Especially 0.05 to 0.5 part by weight is more preferred. When less than 0.0 1 part by weight, the heat resistance improvement effect will be poor, anti-13 -

Η

CH3

nch2ch2ococh2ch2co--och3

(11) (11) 200417591, if it exceeds 1 part by weight, the holding force decreases. (C) Ingredients can also be used in combination of two or more. (D) The component is an organic peroxide hardener, and specific examples are: benzophenylidene peroxide, 4,4'-dimethyldibenzoylidene peroxide, 3,3'-dimethyl Dibenzylidene peroxide, 2,2'-dimethyldibenzylidene peroxide, 2,2 ', 4,4'-tetrachlorodibenzylidene peroxide, cumene peroxide Oxides, etc.

The compounding amount of (D) ingredients is only required to be 0.1 to 5 parts by weight based on 100 parts by weight of the total (A) and (B) ingredients. In particular, 1 to 4 parts by weight is more preferable. If it is less than 0.1 part by weight, the hardenability and retention will be reduced. On the other hand, if it exceeds 5 parts by weight, the adhesive layer may be colored, and the holding power may be reduced. (D) The form of the component is not particularly limited. Generally, it can be a single (D) component, a component in which the (D) component is diluted in an organic solvent, a component dispersed in water 'and a paste dispersed in silicone oil, and the like. (D) Ingredients can be used in combination of two or more. The following are users who can use the addition reaction hardening type polysiloxane adhesive composition. Provided is a polydiorganosiloxane containing (A,) two or more aliphatic alkenyl groups in one molecule. 20 to 80 parts by weight (b) containing RSSiO. "Unit and SiO2 unit 'RSSiO. ”Molar ratio of unit / SiCh unit is a polyorganic 7-oxygen compound with a molar ratio of 0.6 to I.7 (R1 is a monovalent hydrocarbon group with 1 to 100 carbon atoms.) (C) A hindered structure containing the structure shown in the following formula The amine compound is from 0.01 to 1.0 parts by weight based on 100 parts by weight of the total (A) and (B) components (12) (12) 200417591

R

(R is the same as the base shown above.) (E) The polyorganosiloxane containing SiH group is aimed at the aliphatic alkenyl group in the (A,) component, and the molar ratio of the SiH group in the (E) component is 0.5 to The amount of 20 (F) control agent for (A,), (B) total 1,000 parts by weight is 0 ~ 8.0 parts by weight (G) platinum catalyst for (A '), (B) components total as platinum Participants are those with an addition reaction type polysiloxane adhesive composition of 1 to 5 000 ppm. In addition, a feature of the present invention is to provide an adhesive tape in which a hardened layer of the polysiloxane adhesive composition is laminated on at least one side of a plastic film. At this time, these silicone adhesive compositions and adhesive tapes are particularly effective as metal, especially stainless steel color mask tapes. Hereinafter, it will be described in more detail. The component (A ') is a polydiorganosiloxane containing an aliphatic alkenyl group, as shown below.

(3 ^ a) X, si 0- (R4 XS i 0) m-(R4 2S i O) n-S i R4 {3.a) X8 r4 2 (HO) S i 〇 一 (R4 XS i〇) m + 2 — (R4 2S i 〇) n — S i R4 2 (〇H -15- (13) (13) 200417591 (where, R4 is a monovalent hydrocarbon group having no aliphatic unsaturated bond, and x is a fat-containing group) For alkenyl organic groups, a is an integer of 0 to 3, preferably 1, m is 0 or more, η is 100 or more, and a and m cannot be 0 at the same time. Also, m + n is here Polydiorganosiloxane at 25 ° C has a viscosity of 500mPa · s or more. Among them, R4 is preferably a carbon number of 1 to 10, such as: methyl, ethyl, propyl Alkyl groups such as alkyl, butyl, cycloalkyl groups such as cyclohexyl, aryl groups such as phenyl, tolyl, and the like are particularly preferred. Methyl and phenyl are preferred. X is an aliphatic alkenyl-containing organic group. The number is preferably from 2 to 10, such as: vinyl, allyl, hexenyl, octenyl, propenyl propyl, propenyl methyl, methacryl propyl, cyclohexenyl Ethyl, vinyloxypropyl, etc., especially vinyl is industrially preferred. The properties of this polydiorganosiloxane are oily, raw Gelatinous ones are preferred. (A ') Ingredients with oily viscosity at 25 ° C are preferably above 1000mPa · s. Especially above 10,000mPa · s are preferred. When less than 1 OOOmPa · s It is not ideal to reduce the hardenability and the cohesive force (retention). In addition, the viscosity of the raw rubber-like substance when dissolved in 30% toluene is 100,000 mPa · s or less. It exceeds 10,000 niPa · s, the viscosity of the composition is too high for stirring when manufacturing. In addition, the (A) component can be used in combination of more than 2 types. (B) The component contains R ^ SiOo.s units (R3 is the reporter) ) And Si02 units, the molar ratio of R ^ SiOo ”units / Si〇2 units is 0.6 ~ 1.7. If the molar ratio of R ^ SiOo” units / Si〇2 units is insufficient, When it is 0.6, the adhesive force will decrease when both curling, and if it exceeds 1 · 7, the adhesive force will decrease. 16-(14) (14) 200417591 Both the force and holding force will decrease. It may also contain OH groups, and the OH group content is 4.0 weight. It is preferable that the content is less than or equal to%. When the oxo group exceeds 4.0% by weight, the hardenability of the adhesive is not satisfactory. (B) The component may also be used in combination of two or more kinds. Within the range not impairing the characteristics of the present invention, the component (B) may also contain R 1 S i 〇! .5 units, and R 1 2 S i 〇 units. (A ') component, (B) component may also When the (A) component is simply mixed and contains the following formula, R42 (H〇) SiO-(R4XSiO) M + 2-(R42Si) n- Si42 (〇H) (m, n represents the same number as above (R4 is the same as the above base)) (A ') component, (B) component can also be used as a condensation reaction. When the condensation reaction is carried out, a mixture of (A ') and (B) components dissolved in a solvent such as toluene can be reacted by using a basic catalyst at room temperature to reflux, and the combination of (A') and (B) components can be used. It is better than 20/80 ~ 80/20. Especially 30/7 0 ~ 70/30 is more preferable. When the compounding ratio of (A ′) polydiorganosilane is less than 20/80, the adhesive force and holding force are reduced. On the other hand, when it exceeds 80/20, the adhesive force and curling property are reduced. (C) The component is a hindered amine compound, which is the same as the above. (E) The component is a cross-linking agent. There are at least two, preferably three or more hydrogen atoms bonded to silicon atoms in one molecule. Organic hydrogen polysiloxanes can be linear, branched, or cyclic. . The component (E) is as follows, but it is not limited to these. -17- (15) (15) 200417591

HbRVbSiO-CHR'SiOViR ^ S ^ y-SiRVbHb and-(HR1SiO) s- (R12SiO) n (where R1 is the hydrocarbon group, b is 0 or 1, x and y are integers greater than 0, and b is 0, X is 2 or more, and the viscosity of the organic hydrogenated polysiloxane at 25 ° C is 1 to 5,000 mPa · s. S is an integer of 2 or more, t is an integer of 0 or more, and s + tg 3, compared with The best is an integer of 82 s + tg 3) The viscosity of the organic hydrogenated polysiloxane at 25 ° C is preferably 1 to 5,000 mPa · s, and more preferably 5 to 500 mPa · s. It may be a mixture of two or more kinds. When the amount of the (E) component is aimed at the aliphatic alkenyl group in the (a ') component, it is preferable that the SiH-based mole ratio in the (E) component is 0.5 to 20, especially 0.8 to 15. When it is less than 0.5, the cross-linking density is lowered and the holding power is lowered at the same time. Conversely, if it exceeds 20, sufficient adhesion and curling properties cannot be obtained, and the crosslinking density becomes high, which is not desirable. When it exceeds 20, the usable time of the treatment liquid is shortened. (F) The component is a control agent. When the base material of the unmixed polysiloxane adhesive composition is coated, a treatment liquid is added in order to prevent thickening and gelation during heating and hardening. Specific examples: 3 · methyl-1 · butyne-3 -ol, 3 -methyl · 1 · butyne-3 -ol, 3,5-dimethyl-1 -hexyne-3 -ol, 1- Acetylene cyclohexanol, 3--18- (16) (16) 200417591 methyl-3-trimethylsilyloxy-1 · butyne, 3-methyl-3-trimethylsilyloxy- Pivalyne, 3,5-dimethyl-3 -trimethylsilyloxy-1 -hexyne, 1-acetylene-butrimethylsilyloxycyclohexane, bis (2,2-di Methyl-3 -butanoloxy) dimethylsilane, 1,3,5,7 -tetramethyl-1,3,5,7 -tetraethylenecyclotetrasiloxane, 1,1,3,3 -Examples of tetramethyl-1,3-divinyldisiloxane. (F) The compounding amount of the component is preferably 100 to parts by weight of the total (A ') and (B), and is preferably 0 to 8.0 parts by weight, and particularly preferably 0.05 to 2.0 parts by weight. When it exceeds 8.0 parts by weight, hardenability will be reduced. (G) The component is uranium-based catalyst, such as: chloroplatinic acid, an alcohol solution of platinic chloride, a reactant of uranyl chloride and an alcohol, a reactant of chloroplatinic acid and an olefin compound, platinic chloride Examples of reactants with vinyl siloxane. For the total (A ') and (B) components, the platinum content is preferably 1 to 5,000 ppm, and especially 5 to 2,000 ppm is more preferable. If it is less than 1 ppm, it will reduce the hardenability, reduce the crosslinking density, and the retention force. On the other hand, if it exceeds 5,000, it will reduce the usable time of the treatment bath. For the purpose of further improving the heat resistance, a phenol-based antioxidant (Η) may be added to the addition reaction-hardening polysiloxane adhesive. As an example of the (Η) component, it is particularly preferable to have the following structure in the molecule.

-19- (17) 200417591 is described below as a specific example.

H3C CH2A ACH2-h (^ &gt; -CH3 h3c ch2a tBu

Φιι

-20- 200417591

N OMnc Α5 1Ν — tBuA, = OH tRu 〇 = C \ / C = 0IA,

tBu CH2-(〇 &gt;-OH CH2 X ~ 1 tBu CH2 SiO CHa is 0 or more, n is an integer of 1 or more) CHa-Si CHa n CHs For 100 parts by weight of total (A,), (B) components which ( H) The added amount of the component is preferably 0: 1 to 10 parts by weight. When less than 0.1 parts by weight, the residue cannot be effectively prevented at high temperatures. On the other hand, if it exceeds 10 parts by weight, the retention is reduced. In the polysiloxane adhesive composition of the present invention, in addition to the above components, other components can be added arbitrarily. Such as: polydimethylsiloxane, polydimethylsiloxane

-21 · (19) (19) 200417591 Non-reactive polyorganosiloxanes such as Benzene-based Sand Oxygen Plants, such as phenol-based, S-based, amine-based, phosphorus-based, phosphate-based, and sulfur-based Antioxidants such as thioethers, light stabilizers such as diazacene and benzophenone, flame retardants such as phosphate, tooth, phosphine, antimony, etc. Antistatic agents such as ionic active agents. To reduce the viscosity at the time of coating, as the solvent, aromatic solvents such as toluene and xylene, aliphatic solvents such as hexane, Xinyuan, isoparaffin, methyl ethyl ketone, Ketone solvents such as methyl isobutyl ketone, ester solvents such as ethyl acetate, isobutyl acetate, ether solvents such as diisopropyl ether, 1 '4-dioxolane, or mixed solvents, coatings, and pigments Wait. The polysiloxane adhesive composition compounded as described above can be coated on various substrates and cured under predetermined conditions to obtain an adhesive layer. Examples of substrates include polyester, polytetrafluoroethylene, polyimide, polydiphenylene sulfide, polyamidoamine, polycarbonate, polystyrene, polypropylene, polyethylene, and polyvinyl chloride. Examples of composite substrates formed by laminating metal foils such as plastic films, aluminum foils, copper foils, and paper, cloth, and fiberglass such as paper, synthetic paper, and polyethylene laminated paperboard. In order to improve the adhesion between these substrates and the adhesive layer, primer treatment, corona treatment, etching treatment, and plasma treatment can also be used. The coating method can be performed by using known coating methods, such as: fragment coating, lip coating, roller coating, molding coating, doctor blade coating, doctor blade coating, rod coating, Examples include contact coatings, photocopying coatings, screen coatings, dip coatings, and cast coatings. As the coating amount, the thickness of the hardened adhesive layer is 2 ~ 200 μηι -22- (20) (20) 200417591 is suitable, especially 3 ~ 100 μιη is more preferable. As a hardening condition, its peroxide hardening type can be performed at 100 ~ 200 ° C for 30 seconds to 10 minutes, and as an addition reaction type, it can be carried out at 80 ~ 130 ° C for 30 seconds to 3 minutes. Minutes are fine, but it is not limited to this. After coating directly on the substrate as described above, those who manufacture adhesive tapes can also use the release film of the release coating, or apply the coating on the release paper, and then harden it. It is also possible to make adhesive tape. The use of the polysiloxane adhesive composition of the present invention to produce an adhesive tape is not limited to a covering body capable of performing a color mask, and is generally shown below. Such as: stainless steel, copper, iron and other metals, these surfaces are plated, rust-treated metal, glass, ceramics, ceramics, polytetrafluoroethylene, polyfluorene, epoxy resin, phenolic resin for lacquer Equal resins are compounded by these plural compounds. [Examples] Hereinafter, the present invention will be specifically described with reference to examples and comparative examples. However, the present invention is not limited to the examples described below. In addition, the parts in the examples represent 1 part by weight, and the characteristic 値 is measured by the following test method. In addition, Me represents a methyl group, Ph represents a phenyl group, Bll represents a butyl group, and Vi represents a vinyl group [residual property] The thickness of the polysiloxane adhesive solution is 25 μm, and the width is -23- (21) ( 21) 200417591 A 25mm thick polyimide film was cured with a 40 μm thick applicator, and then cured at 130 ° C for 1 minute to make an adhesive tape. This adhesive tape was adhered to a metal plate (honed stainless steel plate), a roller covered with a rubber layer having a weight of 2 kg was repeated once, and then pressure-coated, and then placed in a dryer at 280 ° C. After a predetermined period of time, the metal plate was taken out and cooled to room temperature. After peeling off the adhesive tape, it was observed whether the adhesive layer remained on the surface of the metal plate after the adhesive layer had been aggregated and destroyed. 〇: Peelable without residue: completely residual, X: almost completely residual. [Adhesive force] An adhesive tape was prepared in the same way as the evaluation of the residual property. This adhesive tape was adhered to a stainless steel plate, and a roller covered with a 2 kg rubber layer was repeatedly applied once and then pressure-coated. After standing at room temperature for about 20 hours, the force required to peel the tape from the stainless steel plate (N / 2 5 mm) was measured using a tensile tester at a speed of 300 mm / min at an angle of 180 °. [Retention] An adhesive tape was prepared in the same manner as in the evaluation of retentivity. This adhesive tape was bonded to the lower end of the stainless steel plate with an adhesion area of 25 x 25 mm, and was loaded with a weight of 1 kg at the lower end of the adhesive tape. After being placed vertically at 250 ° C for 1 hour, the disengagement distance was measured with a microscope. [Example 1] -24- (22) 200417591 Mole% of diphenylsilane units with a concentration of 40% dissolved in toluene having a viscosity of 4,200 mPa · s, with 6, the end of its molecular chain Polydimethylsiloxane containing phenyl groups (45 parts) '

Polysand oxygen formed by Me3Si〇 (). 5 units and Si〇2 units

Me3SiO0.5 unit / SiO2 unit = 0.80) 60% of a solution of methylbenzene 丨 valley liquid (92 parts), toluene (30 parts) was heated under reflux while refluxing for 4 hours. After being allowed to cool, a hindered amine compound 1 (manufactured by Asahi Denka Co., Ltd.) was added.

Adecastab LA57) (0.2 parts) and mixed.

ch2coox

I

CHCOOX

I

CHCOOX

CH2COOX is mixed with this mixture (60% of siloxane) (100 parts) and mixed with 50% of polybenzyl peroxide (2.4 parts) and toluene (50 parts) to prepare siloxane parts. Approximately 40% of a polysiloxane adhesive solution. The polysiloxane adhesive was measured for its stickiness, adhesion, and retention. The results are shown in Table [Example 2] A hindered amine compound II (Adecastab LA 5 2 manufactured by Asahi Denka Co., Ltd.) (0.2 parts) was added in place of the hindered amine compound I of Example 1 to prepare a polysiloxane adhesive solution. . -25- (23) (23) 200417591 ch2coox 1 CHCOOX 1 ch3 CH3 n-ch3 CHCOOX | l ^ ch3 ch2coox ch3 Measure the residual properties, adhesion, and retention of this polysiloxane adhesive @ Λ. The results are shown in Table 1. [Example 3] The viscosity dissolved in 30% toluene was 67,000 mPa · s, and the end of the molecular chain was substituted with polydimethylsiloxane (45 parts) blocked by OH group. After the use of methyl polysiloxane, the poly-oxygen j was prepared; the adhesive composition solution was completed. The residual properties, adhesion, and retention of this polysiloxane adhesive were measured. The results are shown in Table 1. [Comparative Example 1] A hindered amine compound I of Example 1 was not added to prepare a polysiloxane adhesive composition solution. The polysiloxane adhesive was measured for its stickiness, adhesion, and retention. The results are shown in Table 1. [Comparative Example 2] A phenol-based antioxidant IΠ (chiba · specialty · (24) 200417591 chemicals company, IRGANOX 1 3 3 0) (0.5 parts) was added in place of the hindered amine compound I of Example 1 to prepare a polymer. Silicone adhesive composition solution. The residual adhesiveness, adhesion, and retention of the polysiloxane adhesive were measured. The results are shown in the table

[Example 4] The viscosity at 30% toluene concentration was 27000 mPa · s, with 15 mol% of methyl vinyl siloxane units and 10 mol% of diphenyl siloxane units. SiMe2Vi-based vinyl and phenyl-containing polydimethylsiloxane (45 parts),

60% toluene solution (92 parts) of polysiloxane (Me3SiO0.fi units / SiO2 units = 0.80) made of Me3SiOG.5 units and Si02 units, and a hindered amine compound is added to the solution made of toluene (30 parts) I (0.2 parts), a crosslinking agent of the following formula (0.16 parts), and acetylene cyclohexanol (0.1 parts) were mixed.

MuSiO — [MeHSi〇] 4. Add SiMe3 to this mixture (60% siloxane) (100 parts), add toluene (50 parts), platinum catalyst CAT-PL-50T (manufactured by Shin-Etsu Chemical Industry Co., Ltd.) (0.5 parts), and mix to prepare Polysiloxane adhesive solution with about 40% siloxane content. The residual adhesiveness and adhesive force of this polysiloxane adhesive were measured -27- (25) (25) 200417591 and holding power. The results are not in Table 1. [Comparative Example 3] The phenol-based antioxidant III (0.5 parts) described above was added instead of the hindered amine compound I of Example 4 to prepare a polysiloxane adhesive composition solution. The residual adhesiveness, adhesion, and retention of the polysiloxane adhesive were measured. The results are shown in Table 1. [Example 5] The viscosity of a 30% cyanocyanine solution when dissolved was 27,000 x nPa · s, with 0.15 mol% of methyl vinyl siloxane units and 10 mol% of diphenyl Siloxane units, the vinyl chain of which is terminated by SiMe2 Vi-based molecular chain and polydimethylsiloxane containing phenyl (45 parts),

60% toluene solution (92 parts) of polysiloxane (Me3SiO0.5 units / Si〇2 units = 0.80) made of Me3SiOG.5 units and Si02 units, and a hindered amine is added to the solution made of toluene (30 parts) Compound I (0.2 parts), phenol-based antioxidant III (0.5 parts), a crosslinking agent of the following formula (0.16 parts) and acetylene cyclohexanol (0.1 parts) were mixed.

Me3Si〇-[MeHSi〇] 4. One SiMes was added with toluene (50 parts), and a platinum catalyst CAT-PL-50T (made by Shin-Etsu Chemical Industry Co., Ltd.) (0.5 parts) was added to the mixture (60% by weight of silicone) (100 parts), and further mixed. Thereafter, a polysiloxane adhesive composition solution having a silicone content of about 40% was prepared. The polysiloxane adhesive was measured for its stickiness, adhesion, and retention. The results are shown in Table 1. -28- (26) 200417591 Retention force E to CD ΙΟ CD 〇 〇 〇00 〇E ooo 〇 〇〇EE CNJ LO LO CO LO CM in CVJ LO C \ J LO T— LO 00 inch 2 180 〇 &lt; &lt;] XX &lt; 〇X 150 〇〇 &lt; 3 XX &lt; 3 〇X c E 120 〇〇〇XX 〇〇X Take 1 诿 o 05 〇〇〇XX 〇〇X o CO 〇〇〇 × <〇〇 &lt; o CO 〇〇〇〇〇〇〇〇 CSJ CM CM IO CM s ~ IO 10 CM CM o 〇〇ο 〇 ^ 〇〇〇 一一 腾 一 = T— CNJ CO τ— CN inch in C0 «uu 鹣 佩- U J-Λ

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Claims (1)

(1) 200417591 Scope of patent application 1. A peroxide-curable polysiloxane adhesive composition, characterized in that it contains (A) 20 to 80 parts by weight of polydiorganosiloxane (B) contains RSSiO. / Units and polyorganosiloxanes with a mole ratio of 0.6 to 1.7 in units of 〇2 units, R'SiOu units / SiO2 units (R1 is a monovalent hydrocarbon group having 1 to 10 carbon atoms) 80 to 20 parts by weight (C) A hindered amine compound containing a structure represented by the following formula is 0.01 to 1.0 part by weight for 100 parts by weight of total (A) and (B) R (R is a monovalent hydrocarbon group having 1 to 6 carbons) (D) organic peroxide hardener for 0.1 to 5.0 parts by weight for 100 parts by weight of total (A), (B) 2. If the scope of patent application is the first The peroxide-curable polysiloxane adhesive composition according to the item, wherein the polydiorganosiloxane is a diphenylsilyloxy unit containing 1 to 35 mol%. 3. An addition reaction type polysiloxane adhesive composition 'characterized by containing 20 to 80 parts by weight of a polydiorganosiloxane having more than two aliphatic alkenyl groups in one molecule (A,) (2) (2 200417591 (B) Contains RSSiO. ”Units and SiO2 units, RSSiO. ”Unit / SiCh unit Polyorganic sand oxygen institute with a molar ratio of 0.6 to 1.7 (V is a monovalent hydrocarbon group with 1 to 10 carbon atoms) 8 0 to 2 0 parts by weight (C) A hindered amine containing a structure represented by the following formula Compound is 0 · 0 1 ~ 1 · 0 parts by weight for 100 parts by weight of total (A,) and (B) R (R is a monovalent hydrocarbon group having 1 to 6 carbon atoms) (E) The polyorganosiloxane containing SiH group is directed to the aliphatic alkenyl group in the (A ') component, and the SiH group molar ratio in the (E) component is 0.5 to Amount of 20 (F) Control agent · For 100 parts by weight of total (A '), (B) 0 to 8.0 parts by weight (G) Platinum catalyst for 100 parts by weight of total (A'), (B) The platinum content is 1 to 5000 ppm. 4. The composition of addition reaction type polysilicone adhesive according to item 3 of the patent application, wherein the polydiorganosilane contains 1 to 35 mole% of diphenylsilyloxy units. ^ 5 If the polysiloxane adhesive composition according to item 3 of the patent application scope, -31-(3) (3) 200417591 makes the component (Η) contain 100 parts by weight (A), (B ) 0.1-10 parts by weight of benzyl antioxidant in total. 6. —An adhesive tape characterized by laminating on at least one side of a plastic film, such as a hardened layer of a silicone adhesive composition composed of the scope of patent application item 1 or 3. -32- 200417591 柒 Ming said that the single abbreviation symbol table is the definitive figure designation table of the original drawing table. If there is no extension J in this case, if there is a chemical formula in this case, please disclose the chemical formula that best shows the characteristics of the invention: None -3-