TW422869B - An organopolysiloxane composition - Google Patents

Abstract

An organopolysiloxane composition comprising (1) 100 parts by weight of an organopolysiloxane having at least two unsaturated groups per molecule, (2) 0.1-30 parts by weight of a liquid organohydrogenpolysiloxane having at least two hydrogen atoms attached directly to silicon atoms (triple bonds Si-H bonds) per molecule, (3) 0.1-6.0 parts by weight of an addition reaction control agent prepared by mixing (a) an acetylene alcohol and (b) a silylated acetylene alcohol in a (b)/(a) ratio ranging from greater than 5 to no greater than 100 on a weight basis, and (4) a catalytic amount of a platinum metal catalyst.

Description

4228 69 A7 _____B7_ V. Description of the invention (1) The present invention relates to a polysiloxane composition, and particularly to an organopolysiloxane composition having excellent stability suitable for forming a peelable hardened film. At present, the release agents using organic polysiloxanes can be classified according to the type of hardening reaction during hardening. Among them, especially the organic polysiloxanes containing alkenyl groups, the organic hydrogenated polysiloxanes, and the thallium-based contacts The formation of a medium, that is, an additional reactive organic polysiloxane composition is most commonly used, and the method is followed by a release agent such as a label or an adhesive tape. At this time, in order to allow the additional reaction of the polysiloxane for release paper, it is necessary to have the ability to suppress the reaction of the platinum catalyst at room temperature and to rapidly perform the alkenyl-containing siloxane and silicon hydride at high temperature. Controlling agent for additional reactions of oxane. There are many proposals for such control agents. Among them, alkynyl alcohols are particularly useful (Japanese Patent Publication No. 44-31476, Japanese Patent Application Publication No. 6-3 29 9 1 7 and Japanese Patent Application Publication No. 9-1 43 37 1 and various publications. ) Seal of the Shellfish Consumer Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs {Please read the precautions on the back before filling this page) In addition, in terms of improving productivity, in recent years, polysiloxane has been required to be cured at high speed and low temperature. There are often proposals to increase the amount of catalyst used. However, although increasing the amount of catalyst can improve the initial hardenability, it has the disadvantage of gelling over time in the treatment bath. In addition, if the amount of catalyst is not specifically increased, as a result of placing the polysiloxane treatment bath at a high temperature for a long time after adding the platinum catalyst, gelation will occur when the catalyst is increased. In addition, when an additional reaction control agent is added to prevent this gelation, there is a disadvantage that the initial hardenability of a product having a longer pot life is reduced. In addition, Japanese Unexamined Patent Publication No. 6-3 2 9 9 1 7 reveals that the long-chain α-alkynyl alcohol is applicable to the Chinese National Standard (CNS) A4 specification (2 丨 0X297 male dragon) 7Z! 4226 69 A7 B7 V. Description of the Invention (2) It is an additional reaction control agent, but • Even if it is used in a small amount and has a long pot life, its initial hardenability will still be reduced. In order to obtain a sufficient control action, examples of such a control agent that do not decrease the hardenability of the polysiloxane composition even if its use is increased are known, for example, a control agent that hydroxysilylates an alkynol (Japanese Patent Application Laid-Open No. 6 1-2 6 1) "But when a large amount of this control agent is used, it does not change the initial hardenability, but it has the disadvantage of reducing the hardenability over time of the treatment bath. In addition, Japanese Patent Application Laid-Open No. 9-143371 discloses that two kinds of control agents with different boiling points are used simultaneously to extend the gelation time of the film. However, this method is used to increase the amount of catalyst or to place it at a high temperature. Under severe conditions such as bath, it is difficult to maintain a sufficient pot life without reducing the hardenability. 6 Therefore, it is very desirable to have a pot life and hardening even when the amount of catalyst is increased or the bath temperature is increased. Controlling agent β, which is bipolar, so the present inventors made a more in-depth study of the current control of alkynols and their silylates, and found that these compounds have the following processes in the polysiloxane treatment bath. Printed by the Central Bureau of Prototype and Consumer Cooperatives (Read the precautions on the back and then fill out this page) First, when acetylenic enzymes are used as control agents, they can be made into the platinum family immediately after being prepared into a treatment bath. The catalyst produces strong coordination | reduces the activity of the catalyst in the treatment bath. Therefore, the activity of the catalyst with acetylenic coordination to the additional reaction will be reduced, but it will not completely stop the additional reaction, but will make the catalyst Carry on Origin of the reaction medium circulated. In addition, the additional reaction of the triple bond of alkynyl alcohol will first be generated in the treatment bath * and then the additional reaction of alkenyl groups in siloxane will be generated, so the paper size will be reduced over time. The Chinese National Standard (CNS} Α4 specification applies (210X297 mm > • 5-Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs 4228 69 A7 B7 V. Description of the invention (3) The amount of alkynyl alcohol is insufficient to control the effect, so the treatment bath will gel. As a result, increasing the amount of alkynols can extend the gelation time. However, if the control action is too long, the initial hardenability will be reduced. As for the silylates of alkynyl alcohols as control agents, Coordination of alkynyl alcohols with platinum group metal catalysts reduces catalyst activity * but * its coordination force is weaker than that of alkynyl alcohols, so its ability to inhibit additional reactions is small *, so silane is generated in the treatment bath The additional reaction of the triple bond of the compound • Although this reaction uses a large amount of silylate, the initial hardenability does not change. Also, there is a large amount of triple bond in the system. Consumption with time S i In this case, the curing time of the treatment bath will be reduced. Therefore, the inventors have inferred that when the two control agents are used, both the pot life and the curing properties can be effective. When combined with a small amount of alkynol and a large amount of silyl compounds, it can have good initial hardenability and the treatment bath with increased catalyst placement will not reduce hardenability over time. Therefore, less peeling characteristics can be obtained The present invention has been completed by changing the composition. Therefore, an object of the present invention is to provide an additional hardened polysiloxane composition which has peelability after hardening, and even if the amount of catalyst is increased or the treatment bath is at a high temperature It is also difficult to change the peeling characteristics and hardenability with time. * A polysiloxane composition having excellent stability. The above-mentioned object of the present invention can be used. The feature is that C1) 1 has at least two molecules in the molecule. 100 parts by weight of saturated polyorganosiloxane. C 2) 1 molecule contains at least 3 hydrogen atom binding threads directly bonded to silicon atoms (please read the note on the back before filling this page) This paper scale Applicable to China National Standard {CNS) A4 specification (210X297 mm) 4228 6 9 Α7 Β7 V. Description of the invention (4) (^ S i Η bond) liquid organic hydrogenated silane 0.1 to 3 parts by weight, (3) 0.06 to 6 parts by weight of a mixture of (a) an alkynyl alcohol having a specific structure and (b) a silylated alkynyl alcohol having a specific structure as an additional reaction control agent, (4) a platinum group of a catalyst amount An organopolysiloxane composition composed of a metal catalyst and having a ratio (b) / (a) of (a) and (b) in the above (3) component of 5 to 100 Reached. Among the (1) components constituting the polysiloxane composition used in the present invention, the organic polysiloxane having at least two alkenyl groups in one molecule is: R2aR3bS i 0 (Buab) / 2 (wherein R2 Is the same or different unsubstituted hydrocarbon group, R3 is a chain group represented by CnH2nCH = CH2 (η is 2 to 6), a is 0 to 3, b is 0 to 3, and a + b is 1 to 3) What is shown. Printed by the Shellfish Consumer Cooperative of the Central Bureau of Standards, Ministry of Economic Affairs (please read the note on the back, and then fill out this page). Also, in this molecule of organic polysiloxane, an alkenyl pair directly bonded to a silicon atom The total organic group is preferably from 0.05 to 50 mol%, and particularly preferably from 0.2 to 10 mol%. If the amount of alkenyl groups is less than 0.05 mol%, a substantial hardening rate cannot be obtained, and when it exceeds 50 mol%, the peeling characteristics are now reduced. Examples of the organic group R2 other than the alkenyl group bonded to the silicon atom are, for example, methyl, ethyl, propyl and alkyl, or phenyl, tolyl and aryl *, or a carbon atom bonded to these groups. Some or all of the hydrogen atoms are replaced by halogen atoms or aryl groups, and may be replaced by the same or different types of groups, or organic groups other than non-substituted aliphatic unsaturated groups. In addition, this bond is in an organic group other than the alkenyl group on the silicon atom, and the Chinese standard (CNS) A4 specification (210X297 mm) is applicable to the amount of methyl groups of all organic groups. The paper size is 4228 6 9 A7 B7 5 2. Description of the invention (5) It is 50 mol% compared with 隹. The organic polysiloxane may be linear or branched, and its terminal may be, for example, any organic group such as a methyl group, a hydroxyl group, an alkenyl group, a phenyl group, or an propylene alkyl group. Base is better. In addition, the viscosity of the organic polysiloxane is preferably 50 c S or more at 25 ° C. The organic hydrogenated polysiloxane of the component (2) of the organic polysiloxane composition used in the present invention is one which contains at least 3 hydrogen atoms bonded to silicon atoms in one molecule, and is appropriately selected from known uses In additional reactive polysiloxane composition. As far as the present invention is concerned, it is particularly preferable to use methyl groups of more than 90 mol% of organic groups. These organic hydrogenated polysiloxanes can be any of linear, branched, and cyclic, and specific examples thereof As shown in the following Chemical 3, [Chemical 3 Η (锖 Please read the notes on the back before filling in this page)

A

, 1T (c h3) 3 s i 〇 i ο-η3 Ο- Η

Si (C Η3), Η Ό —— $ i Η Η, employee cooperation cooperation printed by the Central Bureau of Standards of the Ministry of Economic Affairs Ο C Hs $ i CH3 C Η3 S i C η3 Η This paper standard applies to Chinese National Standard (CNS) A4 specification (210X297 mm) .g. 4228 6 9 A7 B7 V. Description of the invention (6) (C Η 3) 2 S i 0 i 0- h3 0-

H h3 i 0 · H, H3 i 0 H 3 9 i (CH3) 3 or the average composition formula is a co-hydrolysis condensate shown in the following formula 4 (where c and h are integers of 2 or more, d, i, g, i are 0 or positive integers, e, j, k, < are positive integers, h + i = 3 ~ 8), etc. "[Chemical C K 3 S i 0!. s] j CH 3 i 0] k [(CH :) 3 S i 〇〇. {Jing first read the notes on the back before filling this page) The Central Consumer Bureau of the Ministry of Economic Affairs, the Consumer Cooperatives printed these organic hydrogenated polysiloxanes with a viscosity of 25 ° C It can be a wide range from several cs to hundreds of thousands of cs. "As for this (2) the amount of ingredients used may vary depending on the purpose or use of the composition of the present invention, but-generally, the above ingredients (1 100 parts by weight of the organic polysiloxane is preferably 0.1 to 30 parts by weight, and more preferably 20 parts by weight or less. The component (3) used in the present invention is an important component for the present invention, in which the component (a) is an alkynol having a basic skeleton represented by the following formula (5). In Formula 5, R1 and R2 are a hydrogen atom, a linear or branched alkyl group such as methyl, ethyl, propyl, isopropyl, or butyl, or an aryl group such as phenyl or tolyl. This paper standard is applicable to China Standard for Household Standards (CNS) A4 (2 丨 〇2 2mm) 4228 6 9 A7 B7 V. Description of the invention (7) [Chemical formula 5] hc = c- | -oh In addition, R1 and The radical of R2 may form a ring with a carbon atom located at a position for triple bond, and the total number of carbon atoms of R1 and R2 is 8 or less, and particularly preferably 5 or less. If the total number of carbon atoms of R1 and R2 exceeds 8 or more, the initial hardenability will be significantly reduced. The amount of the (a) component varies depending on the amounts of the components (1), (2), and (4). However, it is preferably 0.01 to 1 part by weight based on 100 parts by weight of the (1) component. . 0 parts by weight. When the amount of the component (a) is less than 0.01, the effect of controlling the hardenability cannot be obtained, and when it is more than 1.0, the initial hardenability is lowered. The printed policy of the Shellfish Consumer Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs (please read the precautions on the back before filling this page). Specific examples of the component (a) used in the present invention are, for example, 3-methyl-1-butyne-3— Alcohols (boiling point: 104 ° C), 3-methyl-1 ~ pentyne_3 -alcohols (boiling point: 121 ° C), 3,5-dimethylhexan-3-olefin-1 1-alkyne (boiling point: 103 ° C) , 3 > 5-dimethyl-1, 1-hexyne-1, 3-ol (boiling point 150 ° C), 1-ethynyl-1, 1-cyclohexanol (boiling point 18 0 t), and the like. The component (b) used is a silylated alkynol having the basic skeleton shown in the following formula 6. [化 6] HC = C- ^-〇Si (Rs) a The paper size is applicable to Chinese standards (CNS > A4) (210X297 mm) _ 1〇_ 4228 6 3 A7 B7 _ 5. Description of the invention (8) In Formula 6, R3 and R4 are hydrogen atoms, or linear or branched alkyl groups such as methyl, ethyl, propyl, isopropyl, and butyl, or aryl groups such as phenyl and tolyl. In addition, the bases of R3 and R4 form a ring with carbon atoms located at the triple bond at the α position. The total number of carbon atoms of R3 and R4 is 8 or less. It is particularly preferable that the total number of carbon atoms is 5 or less. When the total number of carbon atoms exceeds 8, the initial hardenability will decrease. In addition, R5 is a linear or branched alkyl group such as methyl, ethyl, propyl, isopropyl, or butyl, or phenyl or tolyl. Isoaryl etc. 0 Specific examples of the (b) component used in the present invention include 'trimethyl (3-methyl-1, butyne-3-hydroxy) silane) (boiling point 1 15 ° C), tetramethyl Tetravinylsilane ring (boiling point above 200 ° C), methyltri (3_methyl_1_ butyne-3_hydroxy) silane (boiling point above 200 ° C), dimethylbis ( 3-methyl-1, butyne-3, hydroxy ) Silane (boiling point 195 ° C), methyl vinyl bis (3-methyl-1-butyne-3-hydroxy) silane (boiling point 200 ° C or more), etc. Although these blending amounts are affected by the amount of ingredients (1), (2), and (4), printed by the Shellfish Consumer Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs (please read the precautions on the back before filling this page), but basically The 100 parts by weight of the component (1) in the upper pair is 0. 06 to 6.0 parts by weight. If the amount of the component (b) is less than 0.6 parts by weight, a sufficient pot life will not be obtained, and when it is more than 6.0 parts by weight, the hardening property of the treatment bath over time will be reduced. In addition, the use ratio of (a) and (b) must be (b) / (a) S 100 »If this ratio is less than 5, and the total use of (a) and (b) is large, it will obviously be Decrease the initial hardenability, as for (a) and (b) this paper size is in accordance with Chinese standards (CNS) A4 Zhuge (210X297 mm). H. Printed by the Bayer Consumer Cooperative, Central Bureau of Standards, Ministry of Economic Affairs «4228 6 9 A7 B7 V. When the total amount of invention description (9) is small, it will be difficult to obtain a sufficient application period. In addition, when the ratio is greater than 100, the hardening property of the treatment bath over time will be reduced. 倂 When these two compounds are used as the control system of the present invention, they have the following action mechanisms. First, after preparing the treatment bath, a small amount of (A) A strong coordination reaction occurs between the alkynol and the catalyst, which reduces the catalyst activity. In addition, the use of only the excess of the silylated alkynol (b) as a substrate for the additional reaction in progress can reduce the decrease in unsilanized alkynyl alcohol. That is, since the silylated alkynol is used as a substrate for the additional reaction, the consumption of the alkynol (additional reaction) can be suppressed. In addition, since the consumption of alkynol can be suppressed in the system, the catalyst can be kept in a low-active state for a long period of time, and therefore, the consumption of S i Η can be suppressed. From the above-mentioned action mechanism, it is known that a composition having a sufficiently long pot life can be obtained even when an alkynol capable of reducing initial hardenability is not used. In the present invention, in order to effectively carry out the additional hardening reaction, it is possible to use, as the component (4), such an additional catalyst such as a platinum group catalyst, which is currently known. Examples of this platinum group catalyst are, for example, platinum-based, palladium-based, rhodium-based catalysts, among which platinum-based catalysts are particularly preferred. Specific examples are, for example, chloroplatinic acid, an alcohol solution or an aldehyde solution of chloroplatinic acid, or coordination compounds of chloroplatinic acid with various olefins, vinylsiloxanes, and the like. Hardened film, the amount of platinum-based catalyst added, that is, the amount of catalyst is preferably • The amount of platinum group metals for components (1) and (2) is 1 ~ 1 | 〇〇〇ppm ppm The polysiloxane of the present invention In addition to the above ingredients, the alkane composition can also be added to this paper. Applicable to China National Standards < CNS > A4 Specification (210X297mm) _ ~ (Please read the precautions on the back before filling this page)

r \ r. 〇 〇 / 1 乙 〇 〇 〇 2; Α7 Β7_ 5. Description of the invention (10) Add other ingredients. For example, in order to adjust the peeling force, if necessary, an organic polysiloxane having no bond with a hydrogen atom on a vinyl group or a silicon atom may be added. As for the addition amount of other components, the effect range of the present invention may not be hindered. Within the appropriate amount. The polysiloxane composition of the present invention can be prepared by blending a certain amount of the above-mentioned components (1) to (4) and other components. In this case, it is preferable to first uniformly mix the components except (4) After all the components are added, the component (4) * is added. If necessary, this composition can be dissolved in an organic solvent such as methyl, xylene, η-hexane, and then used. After the prepared polysiloxane composition is applied to, for example, paper or plastic film, it can be heat-hardened by a general method. This base material forming the cured film of the composition of the present invention is used as a release paper. Because the polysiloxane composition of the present invention contains both, a small amount of an alkynol-based additional control agent that can form a strong coordination on the catalyst and can reduce the catalyst activity, and an excess amount can only be used as an additional reaction The substrate is a silylated alkynol, so it has the advantages of a long pot life and no change in peeling properties and hardening properties after the treatment bath has passed. Printed by the Central Bureau of Standards of the Ministry of Economic Affairs of the People's Republic of China. (Please read the notes on the back before filling out this page.) The following examples and comparative examples will be used to explain the present invention in more detail, but it is not limited to this example. In the example, the parts refer to parts by weight, and the properties in the examples are measured by the following test method. Viscosity of the treatment bath The organic polysiloxane composition of the present invention is adjusted to 30 immediately after preparation. The viscosity at ° C is the initial viscosity, and it is stored at 3 or below for 2 4 hours. The paper size is applicable to China National Standard (CNS) A4 (210X297 mm) 4228 6 9 A7 B7 5. Composition after the invention (11) The viscosity of the material is the viscosity over time. The method of evaluating the hardening property at the early stage of hardening is to prepare the organopolysiloxane composition of the present invention, and then apply it to polyethylene at a pressure of 0 · 6 g / m2. The paper was heated with a hot air dryer at 10 o ° C for a certain period of time to form a hardened film, and it was swiped with your fingers several times in the process to visually check whether it fell off, and finally the time required for hardening was used as the hardenability. Of sclerosing The estimation method is that after the polysiloxane composition of the present invention is stored at 30 ° C for 24 hours, the hardenability is measured according to the method described above. (Read the precautions on the back before filling this page.) The initial peel force is evaluated by preparing the organic polysiloxane composition of the invention, and then immediately forming a coating by measuring the hardenability. Second, at 100 ° C It was allowed to harden for 30 seconds, and then a Tese-7475 tape (manufactured by BDF) was affixed to the surface of the hardened film. Thereafter, heat treatment was performed at 7 Ot for 2 hours, and then a pull tester was used at 180 ° C. The angle and the peeling speed are 0.3 m / min, and the force (g / 2.5 cm) required for peeling is measured as the initial peeling force. The evaluation method of the peeling force over time is 30 ° C. After the organic polysiloxane composition of the present invention is stored for 24 hours, the peeling force is measured by the method described above, and this time is used as the peeling force over time. This paper size applies the Chinese National Standard (CNS) A4 specification (210X297) %) _ -J4-4228 6 9 A7 Central Ministry of Economic Affairs Printed by Zhunzhou Shellfish Consumer Cooperative Co., Ltd. 5. Description of the invention (12) The residual adhesion rate is evaluated at the initial stage by using a polyester film after hardening the organic polysiloxane composition with the same peeling force. Nit_ 3 1 B (Nitto Denko (trade name) product name) affixed to the surface, and then load 20g / cm2, followed by heat treatment at 70 ° C for 20 hours, remove the tape, and then attach this tape On a stainless steel plate, the peeling force (g / 2.5cm) required to remove the tape from the stainless steel plate was measured, and the percentage of the force required to peel the untreated standard tape was compared as the initial residual adhesion rate. . In addition, the evaluation method of the residual adhesion rate over time is: after the organic polysiloxane composition of the present invention is stored at 3 ° C for 24 hours, it is measured in the same manner as above, and the obtained hydrazone is used as the residual adhesion rate over time ^ Example 1 (1) The composition is 0.0075 mol / 100 g of ethylenized system, and when diluted to 30% by weight with toluene, the viscosity is 10, 0 0 0 cp, and the average of the following formula 7 30 parts of a vinyl-containing organopolysiloxane represented by the composition formula was dissolved in 570 parts of toluene. [化 7] (C = C H) 3S i 0 Η = C Η i Ο — Η3 Η 0 Η (Please read the precautions on the back * before filling this page)

Si (C Ηζ = C Η) 3 This paper size is applicable to the Chinese National Standard (CNS) M specification (210 × 297 mm). 15- 4228 6 9 A7 _____B7_ V. Description of the invention (13) (2) The composition is at a viscosity of 250cp SiH valence is 1.02 / 1 0 0 g, 0.65 parts of methyl hydrogenated polysiloxane represented by the average composition formula of the following formula 8 [Chemical formula 8] (C Η 3 S i 0 h3 ° J.

Ha i 0-H3

Si (C H3) filled with Benfen) Secondly, as a component of (3), 3 parts of 3,5-dimethyl-1 -hexyne-3 -alcohol (boiling point 150 ° C) 0.1 parts and as (3 In trimethylsilane (boiling point (2) component, the coordination of alkenylsiloxanes is, in terms of ship conversion, polysiloxane, hardenability, and peeling power are obtained after stirring). 1 of component (b) Dimethylpropynyloxy 1 15 ° C) 0 · 8 parts was added to the above (1) and uniformly mixed. Next, molybdenum and ethyl compounds as the component (4) are added to the above-mentioned polysiloxane in an amount of 2 0 p ppm to the alkane composition 1 »in the above mixture, and the pot life of the obtained composition and The measurement results of the residual adhesion rate are shown in Table 1. The central standard of the Ministry of Economic Affairs of the People's Republic of China printed on the paper is applicable to the Chinese National Standard (CNS) A4 specification (210X297), 16-4228 69 A7.

B. V. Description of the invention (Y) [Table 1] In the initial stage of printing, the Central Laboratories of the Ministry of Economic Affairs, the Consumer Cooperatives, the residual curing adhesive force over time and the residual adhesive force (sec) (g / 2.5cm) ) (%) (cp) (sec) (g / 2.5cm) (%) Example 1 10 23 95 14 25 24 97 Example 2 t 23 100 13 25 23 98 Example 3 20 99 14 20 26 98 Example 4 ί 24 98 13 25 20 98 Example 5 21 100 13 25 20: 100 Comparative Example 1 10 19 100 Gel Comparative Example 2 14 27 98 22 35 38 89 Comparative Example 3 10 17 99 15 45 59 83 Example 6 8 14 98 17 20 36 93 Example 7 14 100 15 20 28 100 Example 8 15 98 22 25 31 93 Example 9 8 14 100 17 20 28 96 Example 10 t 14 98 18 20 30 93 Comparative Example 4 8 12 97 Gel Comparative Example 5 10 16 94 Gel Comparative Example 6 8 14 97 28 35 53 63 (Please read the precautions on the back before filling in this page) -U® Γ This paper size applies Chinese National Standard (CNS ) A4 size (210X297 mm). Manchu-Ministry of Standards and Technology Administration of the People's Republic of China Printed Paper Cooperative 4228 69 Α7 Β7 V. Description of the invention (15) Example 2 Except that the addition amount of (b) 1-dimethylpropynyloxytrimethylsilane in the component (3) was changed to 1.2 parts, the polyacetal oxide composition 2 was obtained in the same manner as in Example 1. The results of the investigation of the properties of the obtained composition 2 are shown in Table 1. Example 3 In addition to (3) component (a) 3,5-dimethyl-hexyne-3-alcohol, the amount of addition was changed to 0.05. Except for the other components, polysiloxane composition 3 was obtained in the same manner as in Example 1. Table 1 shows the results of the investigation of the properties of the obtained composition 3. Example 4 A polysiloxane was obtained in the same manner as in Example 1 except that (a) of the component (3) was changed to 2-methyl-3-butane-2-ol (boiling point: 104 ° C) 0.07 parts.组合 物 4。 Composition 4. The survey results of its characteristics are shown in Table 1. Example 5 A polysiloxane composition 5 was obtained in the same manner as in Example 1 except that (a) of the component (3) was changed to 0.1 part of ethynyl-1-cyclohexanol (boiling point: 19 2 ° C). The survey results of its characteristics are shown in Table 1. Example 6 Except that the amount of component (4) was changed to 4 in the platinum conversion, this paper "Standard Applicable Standard (CNS) A4 Specification (2 丨 〇 × 25» 7mm) ------ ---- f-{Please read the note on the back before filling this page) Order Q. 4228 69 A 7 B7 V. Description of the invention (16) Other than ppm, the polysiloxane composition obtained in Example 1 6. The survey results of its characteristics are shown in Table 1. Example 7 A polysiloxane composition 7 was obtained in the same manner as in Example 2 except that the addition amount of the component (4) was changed to 400 ppm. Table 1 shows the results of the investigation of its characteristics. Example 8 A polysiloxane composition 8 was obtained in the same manner as in Example 3 except that the addition amount of the component (4) was changed to 400 p pm. The results of the investigation of its characteristics are shown in Table 1. Example 9 A polysiloxane composition 9 was obtained in the same manner as in Example 4 except that the addition amount of the component (4) was changed to 400 p p m. The results of the investigation of its characteristics are shown in Table 1. Examination of the properties of the polysiloxane composition 1 obtained in the same manner as in Example 5 except that the addition amount of the component (4) was changed to 400 ppm. The results are shown in Table 1. '' Comparative Example 1 -19- (Please read the notes on the reverse side before filling out this page) This paper size is applicable to the Chinese national standard (CNS > A4 * t (210X297)) 4228 6 9 A7 B7 V. Description of the invention (17) Except that 0.1 part of 3,5-dimethyl-1,1-hexyne-alcohol alone is used as the component (3), the polysiloxane composition 11 obtained in the same manner as in Example 1 is used. 11. The application of the obtained composition The measurement results of the period, the hardening property, the peeling force, and the residual adhesion rate are shown in Table 1. Comparative Example 2 A polysiloxane composition was obtained in the same manner as in Comparative Example 1 except that the amount of the control agent was changed to 0.2 parts. 12. The measurement results of pot life, hardenability, peeling force, and residual adhesion rate of the obtained composition are shown in Table 1. Comparative Example 3 Except changing the control agent and its addition to 1-dimethylpropynyloxy Except for 0.8 parts of trimethylsilane, others were obtained in the same manner as in Comparative Example 1 except for polysiloxane composition 12. The results of measuring the pot life, hardenability, peeling force, and residual adhesion rate of the obtained composition are shown in Table 1. · Comparative Example 4 Printed by the Beibei Consumer Cooperative of the Central and Humble Bureau of the Good Decoration Department. In addition to changing the amount of (4) Except for 400 P pm in platinum conversion, other polysiloxane compositions 14 were obtained in the same manner as in Comparative Example 1. Table 1 shows the measurement results of the pot life, hardenability, peeling force, and residual adhesion rate of the obtained composition. Comparative Example 5 In addition to changing the addition amount of (4) to 400 ppm, its -20- (Please read the precautions on the back before filling this page) This paper scale applies the Chinese standard rate (CNS grid ( 210X297 mm) 4228 6 9 A 7 B7 V. Description of the invention (18) He obtained the polysilazane composition 15 as in Comparative Example 2. Determination of pot life, hardenability, peeling force and residual adhesion rate of the obtained composition The results are shown in Table 1. Comparative Example 6 A polysiloxane composition 16 was obtained in the same manner as Comparative Example 3 except that the addition amount of component (4) was changed to 400 ppm. Pot life, hardenability, and peeling force of the obtained composition The measurement results of the residual adhesion rate are shown in Table 1. The results of the types of control agents, catalyst amounts, and viscosity of the compounds used in the examples and comparative examples are shown in Table 2. {Jing first read the back Please fill in this page for attention.) Sheyinjia • 21-This paper scale is applicable to China's national standard rate {CNS) A4iL (2 丨 0X297) 4228 6 9 A7 B7 h, amendments; V. Description of the invention (a) imi Staff of Intellectual Property Bureau, Ministry of Economy Cooperative printed control agent Catalyst Child Viscosity (CP) Example 1 3,5-dimethyl · 1-hexyn-3-ol 0.1 part 1 14 1-dimethylpropynyloxytrimethylsilane 0.8 part Example 2 0.1 parts each of 3,5-dimethyl 4-hexyne 1 i-dimethylpropynyloxytrimethylsarane 1.2 parts Example 3 3,5-dimethyl-1-hexane Alkyne-3-ol 0,05 parts 1 t 1-dimethylpropynyloxytrimethylsilane 0.8 parts Example 4 Dimethyl-3-butyn-2-ol 0.07 parts 1 1-dimethyl 0.8 parts of propynyloxytrimethylsarane Example 5 0.1 parts of ethynyl-1-cyclohexanol 1 t 1-dimethylpropynyloxydimethylsilane 0.8 parts Comparative Example 1 3,5-dimethyl 0.1 part 1 tyl-1-hexyn-3-ol Comparative Example 2 0.2 part 3,5-dimethyl-1-hexynol 1 Comparative Example 3 1-dimethylpropynyloxytrimethyl 0.8 parts of silane 1 Example 6 3,5-dimethyl + hexyne-3-ol 0'1 part 2 ί 1-dimethylpropynyloxytrimethyl silicon os part Example 7 3,5-dimethyl small hex-3-ol 0.1 part 2 t 1 · dimethylpropynyloxytrimethylsilane 1′2 part Example 8 3,5 · dimethyl · 1 · Hexyne-3 · ol 0.05 parts 2 1 · dimethylpropynyloxytrimethylsilane 0.S parts Example 9 2-methyl-3-butan-2-ol 0.07 parts 2 t 0.8 parts of 1-dimethylpropoxytrimethylsilane Example 10 0.1 parts of ethynyl-1-cyclohexanol 2 t 0.8 parts of 1-dimethylpropynoxytrimethylsarane Comparative Example 4 3 1,5-dimethyl-1-hexyn-3-ol 0.1 part 2 t Comparative example 5 3,5-dimethyl-1-hexyn-3-ol 0.2 part 2 t Comparative example 6 1-dimethyl Propynyloxytrimethylsilane 0.8 parts 2 t (Please read the precautions on the back before filling this page)

f clothing ------- J order I, ------- line A MM public 97 2 X 10 2 (Gage 4) s s) N (c appropriate standard paper used in standard countries

Claims (1)

Announcement X, Patent Application Scope Annex X: Patent Application No. 871 06271 Chinese Application for Patent Scope Amendment March 1989 Amendment 1. An organic polysiloxane composition, characterized by (i) as stated 1000 parts by weight of an organopolysiloxane having at least two unsaturated groups in one molecule represented by the general formula and (Si〇2) in (R1Si〇3 / 2) „(Rl2SiO) p {R ' 3SiO./2)q (m, n, p, q is an integer of 0 or more, R1 is a monovalent hydrocarbon group having no unsaturated group or unsubstituted or substituted unsaturated bond having 1 to 10 carbon atoms) (2) As shown in the following general formula, there are at least three molecules in one molecule. Liquid organic hydrogenated polysiloxanes directly bonded to hydrogen atoms of silicon atoms, 0, 1 to 30 parts by weight, and iSiO :), ( R: Si0 ^ 2) s (R 2: SiO) i (R 2 3SiOu〇u (r.s, t, u is an integer of 0 or more), R2 is a hydrogen atom or a non-carbon number of 1 to 10 Substituted or substituted monovalent hydrocarbon group) (3) As an additional reaction control agent (a) An alkynyl alcohol having the structure of the following formula 1 [化 ί] (Wherein, R1 and R2 are selected from a hydrogen atom and an unsubstituted or substituted monovalent hydrocarbon group having a carbon number of 1 to 10, a phenyl group) and (b) the paper standard having the following formula 2 is applicable to Chinese national standards (CNS) A4 specification (210 X 297 mm)-^! I -------------- Order-, ------- Line | (Please read the back on the back first Please fill in this page for further details.) Ministry of Economic Affairs, Wisdom, Production, Labor and Industrial Cooperation. Fi Printing 4228 6 9 AS BS CS D8 6. Application for Patented Structure Silyl Alkynol [Chemical 2] 1 HCsC-^- 〇Si (Rs) j (In R, R 3 and R 4 are selected from a hydrogen atom 'and unsubstituted or substituted monovalent hydrocarbon group having a carbon number of 1 to 10, and phenyl group, and R 5 is selected from a carbon number of A mixture of 1 to 10 unsubstituted or substituted monovalent hydrocarbon groups, phenyl) 0. 1 to 6. 0 parts by weight and (4) the catalyst is selected from platinum complex or germanium complex The platinum group catalyst is used in the amount of platinum or M metal atom converted to 50 to 10,000 p pm for the component (1), and (a) and (b) of the above (3) component The ratio (b) / (a) is a weight ratio of 5 or more and 1000 or less. 2. The organic polysiloxane composition according to item 1 of the scope of patent application, wherein the carbon number of R 1 and R 2 in Chemical Formula 1 is 8 or less. 3. The organic polysiloxane composition according to item 1 of the scope of patent application, wherein the content of the alkynol component (a) is 100 parts by weight of the component (1), and is 0.01 to 1.0 parts by weight. Range. 4. For example, the organic polysiloxane composition according to the first patent application scope, wherein the carbon number of R3 and R4 of the chemical compound 2 is 8 or less. 5. The organopolysiloxane composition according to item 1 of the scope of the patent application, wherein the unsaturated group of the organopolysiloxane represented by component (1) may have an alkenyl group of -C., (Ri is 0 to 6) indicates. 6. If you apply for the organopolysiloxane composition under the scope of the patent application, please read the note on the back before filling in this page) 'Order-Line · Printed by the Industrial and Commercial Cooperatives of the Intellectual Property Bureau of the Ministry of Economy China National Standard (CNS) A4 specification (210 X 297 public love) -2- 4228 6 9 AS R8 C8 D8 VI. Patent application scope One molecule of the organopolysiloxane shown by the component (1) contains a direct bond Alkenyl groups bound to silicon atoms • The content of the alkenyl group is organic radical aerobic all-silicon, which is a substance for all substituents. Cap. % The earphones of the fighters have Kimo Lishe A ο do what the ••} on the 5th application 2 and even such as > ear 5 • points Mo ο 7% ％ 中 ο its 9 ------- -!! 装 .1! -Order L ------- line. (Please read the precautions on the back before filling out this page.) Employee Cooperation of Wisdom and Time Bureau of the Ministry of Economic Affairs Du printed -3- Size of this paper Applicable to China National Standards < CNS) A4 Specification (210 X 297 MM) Application Date April 23, 1987 Case No. 87106271 Category CnL ^% nt (The above columns are filled by this bureau) A4 C4 422869 ¾ Ministry of Economic Affairs ^ !! 141 ?: Printed by 9 Industrial Consumer Cooperatives | Poor 1 Patent Specification Chinese Organic Polysilazane Composition I >Invention; New Material English An organopolysiloxane composition ： 1) Name of Entering Shinji (2) Nakari Koichi ( 33 Isobe Kenichi Nationality (1) Japanese version 0 Japan (3) Japanese invention 1 tl) Isobe three-to-three-three t-, creative A residence, residence 0 Yoshimoto, Anma, Gunma Prefecture Noden, one eight seven three one two (3) Isobe, Annaka, Gunma Prefecture, Japan Shin-Etsu Chemical Industry Co., Ltd. (Name) Shin-Etsu Chemical Industry Co., Ltd. Nationality (1) Japanese version (1) No.1, No.1, 2-chome, Otemachi, Chiyoda-ku, Tokyo, Japan 3. Applicant's residence, residence (office) Representative Name (1) Jinchuan Chihiro I n tl ^ ^^ 1 · ^^^ 1 n ^^^ 1 κι This paper uses Chinese National Standard (CNS) A4 (210X297 mm) 4228 6 9 A7 B7 h, revised V. Description of the invention (a) imi Printed Control Agent Catalyst Child Viscosity (CP) printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs Example 1 0.1 parts of 3,5-dimethyl · 1-hexyn-3-ol 1 14 1-dimethylpropynyloxytrimethylsilane 0.8 parts Example 2 0.1 parts of 3,5-dimethyl4-hexynyl alcohol 1 part i-dimethylpropynyloxytrimethylsarane 1.2 parts of Example 3 3,5-dimethyl-1-hexyn-3-ol 0,05 parts of 1 t 1-dimethylpropynyloxytrimethylsilane 0.8 parts of Example 4 dimethyl-3 -Butyne-2-ol 0.07 part 1 ί 1-dimethylpropynyloxytrimethylsarane 0.8 part Example 5 ethynyl-1-cyclohexanol 0.1 part 1 t 1-dimethyl 0.8 parts of propynyloxydimethylsilane Comparative Example 1 3,5-dimethyl-1-hexyn-3-ol 0.1 part 1 t Comparative Example 2 3,5-dimethyl-1-hexynol 0.2 part 1 comparative example 3 1-dimethylpropynyloxytrimethylsilane 0.8 part 1 example 6 3,5-dimethyl + hexyn-3-ol 0'1 part 2 1-di Os parts of methylpropynyloxytrimethylsilane Example 7 0.1 parts of 3,5-dimethylhexyl-3-ol 2 t 1 · dimethylpropynyloxytrimethylsilane 1'2 parts Example 8 3,5 · dimethyl · 1 · hexyne-3 · ol 0.05 parts 2 1 · dimethylpropynyloxytrimethylsilane 0.S parts Example 9 2-methyl-3- Butyl-2-ol 0.07 part 2 t 1-dimethylpropoxytrimethylsilane 0.8 part Example 10 Ethynyl-1-cyclohexanol 0.1 part 2 t 1-dimethylpropynyloxytriol 0.8 parts of methylsarane Comparative example 4 0.1 parts of 3,5-dimethyl-1-hexyn-3-ol 2 t Comparative example 5 0.2 parts of 3,5-dimethyl-1-hexyn-3-ol 2 t Comparative Example 6 1-Dimethylpropynyloxytrimethylsilane 0.8 parts 2 t (Please read the precautions on the back before filling this page) f Clothing -------- J Order I,- ----- Line A M 97 2 X 10 2 ( Code 4) Α s) N (c) Standard papers used by moderate standards 4228 6 9 89. I. 3 amendments to touch and charge 丨 B Four Chinese Ministry of Economic Affairs, Intellectual Property Bureau, Consumer Consumption Agency printed abstracts of Chinese inventions ( Title of the invention:) Organic polysiloxane composition The present invention relates to an additional hardened polysiloxane composition that has a peeling property after hardening, and is used to increase the catalyst when the child or the treatment bath is under high temperature , Its peeling characteristics and hardenability with time are not easy to change · In more detail, the present invention is an organic polysiloxane composition, which is (1) at least 2 unsaturated in 1 molecule Based on 100 parts by weight of organic polysiloxanes (2) Liquid organic hydrogenated polysiloxanes containing at least 3 hydrogen atoms (= S 丨 Η bonds) directly bonded to silicon atoms in a molecule of 0.1 ~ 30 parts by weight, (3) (a) an alkynyl alcohol having the structure of the following formula 1 as an additional reaction control agent, and [chemical formula HC -OH English Abstract of the Invention (Name of the Invention: An organopolysiloxane composition) An organapolysiloxane con ^ osition coo ^ rising (X) 100 parts by weight of an organopolysiloxane having at least two unsaturated groapa per molecale, (2) 0.1-30 parts by weight of a liquid organohydrogenpolysiloxane having at least two hydrogen atoms attached directly to silicon atoms (SSi-H bonds) per molecule, (3) 0.1-6.0 parts by weight of an addition reaction control agent prepared by mixing (a) an acetylene alcohol 【 I] HC = C ~ OH nz This paper uses China National Standards (CNS) A4 size (2l0xW7mm) I .-- ^ ------- ^ -Packing ------- --Order ----- / Line {Please read the notes on the back before filling out the columns on this page) 4228 69 A5 B5 IV. Abstract of the Chinese Invention (Name of the invention: (b) It has the structure of the following formula 2 and A The ratio of the silylated alkynyl alcohol [H2] HCsC-C-OS i (Rs), ο · formed by the catalyst) (b / family and pin} * the amount of a under {in the medium ο contact Middle ο} points 1 40% on C}, 35 parts {specific amount t ff «3 ^ απ 0 ,, • External is M6 and other} 1 · 3 (Please read the notes on the back before filling in the columns on this page) * Install the English abstract (name of the invention:) and (b) a silylated acetylene alcohol in a (b) / (a) ratio ranging from grea -her -than 5 to no greater than 100 on a weight -basis, and (4) a catalytic aiaount of platinna metal catialys ^. a Order printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs [化 2] HC = C- y -〇Si (R5) 3 R * In the paper size, the national kneading rate (CNS) A4 (210X297 mm) -2-1 Announcement X, Patent Application Scope Annex X: Patent Application No. 871 06271 Chinese Application for Patent Scope Amendment March 1989 Amendment 1. An organic polysiloxane composition, characterized by (i) as stated 1000 parts by weight of an organopolysiloxane having at least two unsaturated groups in one molecule represented by the general formula and (Si〇2) in (R1Si〇3 / 2) „(Rl2SiO) p {R ' 3SiO./2)q (m, n, p, q is an integer of 0 or more, R1 is a monovalent hydrocarbon group having no unsaturated group or unsubstituted or substituted unsaturated bond having 1 to 10 carbon atoms) (2) As shown in the following general formula, there are at least three molecules in one molecule. Liquid organic hydrogenated polysiloxanes directly bonded to hydrogen atoms of silicon atoms, 0, 1 to 30 parts by weight, and iSiO :), ( R: Si0 ^ 2) s (R 2: SiO) i (R 2 3SiOu〇u (r.s, t, u is an integer of 0 or more), R2 is a hydrogen atom or a non-carbon number of 1 to 10 Substituted or substituted monovalent hydrocarbon group) (3) As an additional reaction control agent (a) An alkynyl alcohol having the structure of the following formula 1 [化 ί] (Wherein, R1 and R2 are selected from a hydrogen atom and an unsubstituted or substituted monovalent hydrocarbon group having a carbon number of 1 to 10, a phenyl group) and (b) the paper standard having the following formula 2 is applicable to Chinese national standards (CNS) A4 specification (210 X 297 mm)-^! I -------------- Order-, ------- Line | (Please read the back on the back first (Please fill in this page again for the matters needing attention.)